Multilayer films with quiet film layer having noise dampening properties

ABSTRACT

Multilayer films comprising a quiet film layer having noise dampening properties and at least one second layer which are particularly useful for, ostomy bags (colostomy, ileostomy), trans-dermal delivery systems (TDDS), cosmetic patches, incontinence bags, medical collection bags, parenteral solution bags, and food packaging, as well as for protective clothing and soil fumigation applications. The quiet layer comprises a polymer resin or polymer resin composition having a Tangent Delta value of at least 0.25 at a temperature within the range of −5° C. and 15° C. or at least 0.32 at a temperature within the range of −12° C. to −5° C., and the at least one second layer has a storage modulus G′ equal to or greater than 2×10 4  N/cm 2 .

CROSS REFERENCE STATEMENT

This application is a Divisional of U.S. application Ser. No.09/605,496, filed Jun. 28, 2000, U.S. Pat. No. 6,455,161, which claimsthe benefit of U.S. Provisional Application No. 60/141,744, filed Jun.30, 1999, now abandoned.

This invention relates to essentially amorphous, non-chlorinatedpolymeric films and to the use of such films as effective barriers toodors and organic molecules.

Multilayer structures, which are substantially impervious to gasesand/or moisture, are well known in the medical and food packagingindustries. Currently, poly(vinylidene chloride) (PVDC) is used as oneof the materials of choice for the gas barrier component of barrierfilms. For ostomy applications (i.e., colostomy and ileostomy), a filmof PVDC sandwiched between opposing layers of low density polyethylene(LDPE) is widely used, with PVDC functioning as the gas barrier, andLDPE as the structural and sealant layer. Also, polyvinyl chloride (PVC)or chlorinated polyethylene (CPE) blended with ethylene-vinyl acetatecopolymer (EVA) can be used in the structural and sealant layer, orother layers, of such a structure.

However, disposal of these chlorine-containing materials presents anumber of potential environmental concerns, especially relating toincineration of these materials after use in hospitals or otherwise. Inaddition, exposure to di-2-ethylhexyl-phthalate (DEHP), a commonplasticizer utilized with PVDC and PVC, may present a number ofhealth-related concerns, including reduced blood platelet efficacy, andpotential links to liver cancer.

Non-chlorine containing polymeric resins, such as ethylene-vinyl alcoholcopolymers (EVOH), are also used as barrier layers and have beensuggested for ostomy applications. However, while the barrier propertiesof EVOH copolymers are very high under dry conditions, they rapidlydeteriorate in the presence of moisture. Thus, EVOH copolymers are notdesirable for ostomy applications.

U.S. Pat. No. 5,496,295, U.S. Pat. No. 5,658,625 and U.S. Pat. No.5,643,375 describe multilayer barrier films and articles made thereof.These films are useful, among others, in ostomy applications, andcomprise a gas barrier layer of a chlorine-free organic polymer, whichis substantially impermeable to oxygen gas, and a moisture barrier layerof a mesophase propylene-based material. The chlorine-free organicpolymer gas barrier layer includes vinyl alcohol polymers, such as EVOHcopolymers, polyvinyl alcohol (PVOH), polyacrylonitrile, polystyrene,polyester and nylon either alone or blended with each other. Themoisture barrier layer comprises a mesophase propylene polymer-basedmaterial, such as mesomorphous polypropylene, mesopolymer blends and/ormesocopolymers. Quenching a propylene-based material from the melt stateforms the mesophase propylene-based material.

EP 0 700 777 A1 describes a chlorine-free multilayer film useful formanufacturing bags or pouches for ostomy/urostomy applications andcomprising a seven layer structure. This structure comprises a gasbarrier layer of a chlorine-free organic polymer which is substantiallyimpermeable to oxygen, such as one of the above vinyl alcohol polymers,polyamides, polyesters and polystyrenes; two tie layers each contactingone side of said barrier layer; an inner surface layer; an outer surfacelayer and two intermediate layers positioned between said surface layersand comprising an ethylene-propylene (EP) copolymer.

EP 0 418 836 A3 describes multilayer oriented films suitable for use inthe food packaging industry and having layers of a propylene homopolymeror copolymer, a co-polyester layer and an adhesive layer of apolar-modified polyolefin located between, and bonded to, the propylenepolymer and co-polyester layers.

EP 0 056 323 A1 describes a thermoformable laminate for a sterilizablepackaging comprising a cast layer of polyester, including polybutyleneterephthalate, glycol-modified polyethylene terephthalate (PET-G), and acopolymer of cyclohexane dimethanol and terephthalic acid, joined by abonding layer consisting of polypropylene (PP), LDPE or an ionomerresin. However, since such structures are targeted for thermoformablepackaging applications, they possess high modulus and, therefore, cannotprovide the required level of quietness needed for ostomy bagapplication as a result of the relatively rigid polymers used for skinscomposition. Additionally, the Tangent Delta (Tan Δ) value of the skinpolymers (LDPE, crystalline PP and ionomer resins) of these laminatesindicate that they do not provide a quiet film as described below.

EP 0 588 667 A2 describes a multilayer film useful in moisture barrierpackaging applications having at least one layer comprising a blend ofpropylene polymer or copolymer and a hydrocarbon resin and twoadditional layers comprising a propylene homopolymer or copolymer, anethylene-alpha-olefin (EAO) copolymer, an ionomer, polybutylene orblends thereof. A core layer of an EVOH copolymer or another oxygenbarrier material or high density polyethylene (HDPE) can be included insome embodiments.

Attempts to find additional chlorine-free polymeric films suitable foruse as barrier layers have been guided by a generally held belief that apolymer having good oxygen barrier properties would also exhibit goodbarrier properties to organic products and odors. (See, for example,“Plastic Film Technology, High Barrier Plastic Films for Packaging”,volume 1: The use of Barrier Polymers in Food and Beverage Packaging, M.Salame, pp. 132-145 (1989)). Therefore, attempts to find polymeric filmswith sufficient barrier properties for use in the medical andfood-packaging industries have focused upon the oxygen permeability of agiven polymeric film. However, the inventors of the present applicationhave found that not all polymers having low oxygen permeability exhibitodor barrier properties sufficient for ostomy applications and viceversa.

Studies have shown that human feces contain more than 122 volatilecompounds as analyzed by gas chromatography/mass spectrometry. (See“Identification of Specific Trace Levels of Chemicals in Human Feces”,Dmitriev M. T., Lab. Delo (1985), (10), 608-14; “Gas-Chromatographic andMass-Spectrometric Analysis of the Odour of Human Feces”, J. G. Moore,Gastroenterology, 1987, 93, 1321-9; M. D. Levitt, “Only the Nose Knows”,Gastroenterology, 1987, vol. 93, No. 6, 1437-8; “Influence ofNutritional Substrates on the Formation of Volatiles by the FecalFlora”, M. Hiele, Gastroenterology, 1991, 100, 1597-1602; “ScreeningMethod for the Determination of Volatiles in Biomedical Samples”; Y.Ghoos, Journal of Chromatography, 665, 1994, 333-345; and “Influence ofDietary Protein Supplements on the Formation of Bacterial Metabolites inthe Colon”, B. Geypens, GUT, 1997, 41, 70-76.)

These studies indicate that compounds responsible for fecal odor aremainly indoles and sulfide derivatives. Thus, compounds havingrelatively small molecules, such as, for example, hydrogen sulfide (H₂S)or methyl mercaptan (CH₃SH), compounds having larger molecules, such as,for example, ethyl sulfide, dimethyl disulfide (DMDS) or diethyldisulfide (DEDS), and compounds having large molecules, such as, forexample, dimethyl trisulfide, indole or 3-methyl indole, are responsiblefor fecal odor.

Therefore, there remain needs in the art for polymeric films which (a)are environmentally safe, (b) are hydrolytically stable, and (c) exhibitlow permeability to both small and larger molecular diameterodor-causing molecules. Furthermore, depending upon the end-use of suchfilms, there remains the need for these films to be quiet, i.e., havinglow noise emission when crumpled.

Those needs are met by the present invention. Thus, the presentinvention provides essentially amorphous, non-chlorinated (orchlorine-free) polymer films useful as barriers to odors and organiccompounds, as well as methods of using such films as barriers to odorsand organic molecules in a monolayer or a multilayer film structure.

A first embodiment of the present invention is an essentially amorphous,non-chlorinated polymer film, the film functioning as a barrier to atleast one of odors and organic molecules that have a diameter of 0.40nanometer (nm) or more (≧) with barrier functionality being determinedby at least one of a) a 3-methyl indole breakthrough time of at least(≧)five hours, b) a DEDS breakthrough time of at least 40 minutes (min) orc) a H₂S permeation rate less than or equal to (≦) 60 cubic centimeters(cm³) of H₂S per square centimeter (cm²) of film area per day(cm³/cm²-day), as well as a method of using such films as barriers toodors and organic molecules in either a monolayer or a multilayer filmstructure.

A second embodiment provides multilayer film structures containing≧onelayer of the film of the first aspect and ≧one quiet film layer that hasreduced noise emission, said quiet film layer comprising ≦one polymericresin or polymeric resin composition having a Tan Δ value ≧0.25 at atemperature within the range between −5° centigrade (° C.) and 15° C.,or ≧0.32 at a temperature within the range of from −12° C. to −5° C. Themultilayer film structures desirably function as barriers to moleculeshaving a diameter≧0.40 nm.

A third embodiment provides a method of reducing the emission of noisein a multilayer film structure containing≧one layer of the film of thefirst embodiment, the method comprising the steps of: a) blending afirst polymer resin, polymer resin composition or polymer blendcomposition having a Tan Δ value ≧0.25 at a temperature within the rangebetween −5° C. and 15° C. or ≧0.32 at a temperature within the range offrom −12° C. to −5° C. with a second polymer resin; and b) forming apolymer film layer of the multilayer film from the blended polymerresins, wherein the first polymer resin or polymer resin compositioncomprises ≧25 percent by weight (wt %), based on total layer weight.

The polymeric barrier films of the present invention are particularlyuseful for ostomy bags (colostomy, ileostomy), trans-dermal deliverysystems (TDDS), cosmetic patches, incontinence bags, medical collectionbags, parenteral solution bags, and packaging of odorous food orproducts, as well as for protective clothing applications or soilfumigation.

As stated above, the present invention provides essentially amorphous,non-chlorinated polymer films, which are useful as barriers to odors andorganic compounds, as well as methods of using such films, in amonolayer or multilayer film structure, as barriers to odors and organicmolecules.

As used herein, “essentially amorphous” means containing less than (<) 8wt % non-amorphous polymer(s), based on total polymer weight. Moreover,it refers to amorphous polymers that have not been prepared throughquenching. “Quenching”, as used herein, means rapid cooling of thepolymer from its melt state down to a sub-ambient temperature (belowapproximately 20° C.). “Non-chlorinated” means that a polymer containssubstantially no chlorine (i.e., <1 wt %, based on total polymerweight).

The terms “relatively small”, “larger” and “large” molecules, as usedherein, refer to relative sizes as determined by respective criticalmolecular diameter (CMD). “Relatively small” molecules include moleculeshaving a CMD of 0.40 nm up to 0.55 nm. “Larger” molecules includemolecules having a CMD of more than (>) 0.55 nm and up to 0.70 nm, and“large” molecules include molecules having a CMD >0.70 nm.

The calculated CMD of oxygen is 0.33 nm, 0.40 nm for H₂S, 0.50 nm formethyl sulfide, 0.55 nm for DMDS, 0.57 nm for ethyl sulfide, 0.58 nm forDEDS, 0.63 nm for dimethyl trisulfide, 0.74 nm for indole and 0.78 nmfor 3-methyl indole. CMD determination uses a SPARTAN 5.1.1. program(molecular orbital program marketed by WAVEFUNCTION Inc., California92612, USA).

Molecular structures are optimized by energy minimization usingsemi-empirical quantum mechanics models (AM1 method: M. J. S. Dewar, E.G. Zoebisch, E. F. Healy, and J. J. P. Stewart, J. Am. Chem. Soc. 107,3902 (1985). AM1: A New General Purpose Quantum Mechanical Molecular)contained in the Spartan program version 5.1.1. Conformational analysisis carried out in order to obtain structures in their minimum-energyconformations. The CMD is obtained from the space-filling (CPK)representation of the optimized structure. The box size is adjusted inorder to contact the van der Waals spheres. The molecular diameter istaken as the second-largest box dimension.

However, while a given polymeric film's low oxygen permeability may be areasonable predictor of the polymeric film's low permeability to thesmaller odorous molecules in human fecal matter, such as H₂S and CH₃SH,such permeability may not be a reasonable predictor of the polymericfilm's permeability to larger molecules, such as DEDS and 3-methylindole. Hence, the inventors of the present application believe that agiven polymeric film's low oxygen permeability does not provide areasonable predictor of the usefulness of the polymer film in ostomyapplications. The permeabilities to H₂S, DEDS and 3-methyl indole areselected to predict the odor barrier performance in ostomy applications,as these three compounds represent the main chemical families of odorouscompounds found in feces, and cover a range from relatively small tolarge molecule sizes.

In the present invention, it has been found that polymer films thatfunction as a barrier to molecules having a CMD ≧0.40 nm can be formedfrom, but are not limited to, polymeric resins pertaining to PolymerList I. Polymer List I comprises: polymethyl methacrylates (PMMA),PET-G, an amorphous thermoplastic co-polyester resin (e.g. B-100 resinsupplied by Mitsui Chemicals Europe GmbH) (hereinafter referred to as“APE-1”), blends of PET-G and such an amorphous thermoplasticco-polyester resin, blends of PET-G and a styrene-butadiene copolymer(PET-G/SB), blends of PET-G and a styrene-butadiene-styrene blockcopolymer (PET-G/SBS), blends of PET-G and a maleic anhydride (MAH)grafted ethylene-methyl acrylate copolymer (PET-G/MAH-g-EMA), blends ofPET-G and an ethylene-methyl acrylate-glycidyl methacrylate copolymer,blends of PET-G and a MAH functionalized styrene-ethylene-butene-styrene(PET-G/SEBS) block copolymer, blends of PET-G and astyrene-isoprene-styrene (PET-G/SIS) block copolymer, and amorphousthermoplastic polyester resins having a glass transition (T_(g))temperature >50° C., amorphous polyamide or copolymer polyamide having aT_(g)≦120° C., epoxies, amorphous polyurethanes and blends thereof with≧60 wt % PET-G are especially useful as barriers to molecules having adiameter≧0.40 nm, with PET-G and PMMA being especially preferred.

When preparing the essentially amorphous, non-chlorinated polymericbarrier films from blends such as exemplified above, the minor blendcomponent need not be amorphous, but may be a semi-crystalline polymer.The definition of amorphous and semi-crystalline polymers can be foundin the “Polymer Science Dictionary”, 1989 edition, Elsevier AppliedScience. It should also be understood that when the essentiallyamorphous, non-chlorinated polymeric barrier films are prepared fromblends such as exemplified above, the major blend component, i.e.,PET-G, constitutes ≧60 wt % of the blend. Typical examples of suchblends are the following: 1) 70 to 95 wt % of a blend of PET-G and a SBcopolymer; 2) 60 to 90 wt % of a blend of PET-G and a SBS blockcopolymer; 3) 70 to 96 wt % of a blend of PET-G and a MAH-g-EMAcopolymer; 4) 70 to 96 wt % of a blend of PET-G and an ethylene-methylacrylate-glycidyl methacrylate copolymer; 5) 70 to 96 wt % of a blend ofPET-G and a MAH functionalized SEBS block copolymer; and 6) 70 to 96 wt% of a blend of PET-G and a SIS copolymer.

Blends of PET-g and an amorphous thermoplastic polyester resin such asAPE-1 readily replace PET-G alone. Such blends have an APE-1 contentthat is desirably 0-100 wt %, preferably 10-80 wt % and more preferably20-70 wt % and, conversely, a PET-G content that is desirably 100-0 wt%, preferably 90-20 wt % and more preferably 80-30 wt %. In eachinstance, the percentages total 100 wt %, with all percentages based onblend weight.

It has been found that it is critical that the essentially amorphous,non-chlorinated polymeric barrier films according to the presentinvention which are a barrier to molecules having a diameter≧0.40 nm,also possess a H₂S permeation rate of ≦60 cm³/m²-day.

The polymeric barrier films of the present invention which are barrierto molecules having a diameter≧0.55 nm include, but are not limited to,films formed from Polymer List I and Polymer List II. Polymer List. IIcomprises: styrene-acrylonitrile (SAN) copolymers, blends of a SANcopolymer and an ethylene-styrene interpolymer (SAN-ESI),acrylonitrile-butadiene-styrene (ABS) terpolymer; impact-modifiedpolymethyl methacrylate (PMMA-IM); polycarbonate (PC); impact-modifiedpolycarbonate (PC-IM); and PC and ABS (PC/ABS) terpolymer alloy.

The polymeric barrier films of the present invention which are barrierto molecules having a diameter≧0.70 nm include, but are not limited to,films formed from Polymer Lists I, II and III. Polymer List IIIcomprises: polystyrenes, including general purpose polystyrenes (GPPS),high impact polystyrenes (HIPS), blends of GPPS and HIPS (GPPS/HIPS),blends of GPPS and a SB copolymer (GPPS/SB), blends of GPPS and ESI(GPPS/ESI), and blends of GPPS and SIS block copolymer (GPPS/SIS).Amorphous polyamides and co-polyamides having a T_(g)>120° C. are notwithin the scope of the present invention.

Examples of essentially amorphous, non-chlorinated polymeric barrierfilms prepared from blends of Polymer Lists II or III above may comprisethe components of the blend in any proportion, but typically asfollows: 1) 60 to 95 wt % of a blend of SAN copolymer and ESI; 2) 30 to70 wt % of a blend of GPPS and HIPS; 3) 60 to 90 wt % of a blend of GPPSand SB copolymer; 4) 60 to 90 wt % of a blend of GPPS and ESI; and 5) 60to 90 wt % of a blend of GPPS and SIS block copolymer.

The aforementioned ESI is a substantially random interpolymer comprisingin polymerized form i) ≧one alpha-olefin (α-olefin) monomer and ii) ≧onevinyl or vinylidene aromatic monomers and/or ≧one sterically hinderedaliphatic or cycloaliphatic vinyl or vinylidene monomers, and optionallyiii) other polymerizable ethylenically unsaturated monomer(s).

The term “interpolymer” is used herein to indicate a polymer wherein≧two different monomers are polymerized to make the interpolymer.

The term “substantially random” in the substantially random interpolymerresulting from polymerizing i) ≧one olefin monomer and ii) ≧one vinyl orvinylidene aromatic monomer and/or ≧one or more sterically hinderedaliphatic or cycloaliphatic vinyl or vinylidene monomers, and optionallyiii) other polymerizable ethylenically unsaturated monomer(s) as usedherein generally means that the distribution of the monomers of saidinterpolymer can be described by the Bernoulli statistical model or by afirst or second order Markovian statistical model, as described by J. C.Randall in POLYMER SEQUENCE DETERMINATION, Carbon-13 NMR Method,Academic Press New York, 1977, pp. 71-78. Preferably, such substantiallyrandom interpolymers do not contain more than 15% of the total amount ofvinyl or vinylidene aromatic monomer in blocks of vinyl or vinylidenearomatic monomer >than 3 units. More preferably, the interpolymer is notcharacterized by a high degree of either isotacticity orsyndiotacticity. This means that, in the carbon-13 NMR spectrum of thesubstantially random interpolymer, peak areas corresponding to the mainchain methylene and methine carbons representing either meso diadsequences or racemic diad sequences should not exceed 75% of the totalpeak area of the main chain methylene and methine carbons. Thesubsequently used term “substantially random interpolymer” or “SRIP”means a substantially random interpolymer produced from theabove-mentioned monomers.

Suitable olefin monomers which are useful for preparing a SRIP include,for example, olefin monomers containing from 2 to 20 (C₂₋₂₀), preferablyfrom 2 to 12 (C₂₋₁₂), more preferably from 2 to 8 (C₂₋₈) carbon atoms.Particularly suitable are ethylene, propylene, butene-1,4-methyl-1-pentene, hexene-1 or octene-1 or ethylene in combination withone or more of propylene, butene-1, 4-methyl-1-pentene, hexene-1 oroctene-1. Most preferred are ethylene or a combination of ethylene withC₃₋₈-α-olefins. These alpha-olefins (α-olefins) do not contain anaromatic moiety.

Other optional polymerizable ethylenically unsaturated monomer(s)include strained ring olefins such as norbornene and C₁₋₁₀ alkyl orC₆₋₁₀ aryl substituted norbornenes, with an exemplary interpolymer beingethylene/styrene/norbornene.

Suitable vinyl or vinylidene aromatic monomers, which can be employed toprepare a SRIP , include, for example, those represented by thefollowing Formula I

wherein R¹ is selected from the group of radicals consisting of hydrogenand C₁₋₄ alkyl radicals, preferably hydrogen or methyl; each R² isindependently selected from the group of radicals consisting of hydrogenand C₁₋₄ alkyl radicals, preferably hydrogen or methyl; Ar is a phenylgroup or a phenyl group substituted with from 1 to 5 substituentsselected from the group consisting of halo, C₁₋₄-alkyl, andC₁₋₄-haloalkyl; and n has a value from zero to 4, preferably from zeroto 2, most preferably zero. Particularly suitable such monomers includestyrene and lower alkyl- or halogen-substituted derivatives thereof.Preferred monomers include styrene, α-methyl styrene, the lower (C₁₋₄)alkyl- or phenyl-ring substituted derivatives of styrene, such as forexample, ortho-, meta-, and para-methylstyrene, t-butyl styrene, thering halogenated styrenes, such as chlorostyrene, para-vinyl toluene ormixtures thereof. A more preferred aromatic monovinyl monomer isstyrene.

The most preferred substantially random interpolymers are interpolymersof ethylene and styrene and interpolymers of ethylene, styrene and ≧oneC₃₋₈ α-olefin.

The SRIPs usually contain from 0.5 to 65, preferably from 1 to 55, morepreferably from 2 to 50 mole percent (mol %) of ≧one vinyl or vinylidenearomatic monomer and/or sterically hindered aliphatic or cycloaliphaticvinyl or vinylidene monomer and from 35 to 99.5, preferably from 45 to99, more preferably from 50 to 98 mol % of ≧one C₂₋₂₀ aliphatic olefin.SRIPs can be prepared according to WO98/10014 and its US equivalentsU.S. Pat. No. 5,703,187 and U.S. Pat. No. 5,872,201, the relevantteachings of which are incorporated herein by reference.

The barrier films of the present invention may contain one or more ofthe following additives: processing aids, such as fluoropolymers,silicones or siloxanes; inorganic fillers such as barium sulfate,calcium carbonate, mica, silica, silica gel, nanofillers and talc; slipadditives such as fatty acid amides; antiblock additives; odorabsorbers; humidity absorbers; molecular sieves; pigments; antistaticadditives; antifog agents; antioxidants; UV stabilizers; dielectricheating sensitizing additives; pigments; colors; activated carbon;fragrance; nucleating agents, clarifiers; biocides and antimicrobialadditives. The additives may optionally be encapsulated inmicrogranules. At least one outside layer of the film may be subjectedto a surface treatment such as corona treatment or flame treatment orplasma treatment to increase its surface tension and improve itsprintability. Optionally, ≧one surface of the film may also be coatedwith a thin layer of metal or metal oxide such as aluminum, aluminumoxide, or silicon oxide.

At least one surface of the film can be embossed or texturized toimprove resistance to blocking, machinability, or handleability or toimpart some performance benefit like softness, suppleness or appearance.

The essentially amorphous, non-chlorinated polymeric barrier films usedin accordance with the present invention as barriers to odors andorganic molecules may be used as single or monolayer films or as acomponent film of a multilayer film structure. Examples of themultilayer film structures comprise, but are not limited to, 2 to 7layers and could, for example, take the form of A/B/D/C/D/E/F orA/B/C/B/A or A/B/C/D/E or A/B/C/D, or A/C/B/, or C/B, with the “C” layerbeing the essentially amorphous, non-chlorinated polymeric film layer ofthe present invention, with the other layers comprising adhesive,intermediate or skin layers. Multilayer film structures having more thanone “C” layer, i.e., odor barrier layer, are also contemplated.

When the essentially amorphous, non-chlorinated polymeric films are usedas single- or monolayer barrier films, the film has a thickness thatdepends upon the intended end-use of the film as well as the individualodor and organic compound barrier properties of the films. However, thethickness typically ranges from 5 to 50 micrometers (μm), with from 10μm to 25 μm being more typical, and from 12 μm to 20 μm being mosttypical. Although any essentially amorphous, non-chlorinated polymericbarrier film useful in the present invention may be used as a monolayerfilm, multilayer films of essentially amorphous, non-chlorinatedpolymers are also contemplated.

The monolayer barrier films of the present invention are prepared byconventional techniques, such as by extrusion, blowing, or casting, withextrusion being preferred. The barrier films of the present inventionare also non-oriented films.

When not pigmented, not embossed and uncoated, the barrier films of thepresent invention are also transparent as defined by a haze value ≦45%,measured according to American Society for Testing and Materials (ASTM)test D1003. If haze is not important, the use of one or more of pigmentaddition, embossing, coating, or inclusion of other additives will notalter the scope of the present invention.

When the essentially amorphous, non-chlorinated polymeric barrier filmsare used as component films of a multilayer film structures, theessentially amorphous, non-chlorinated polymeric barrier film whichprovides the odor and organic compound barrier properties to themultilayer film structure typically has a thickness of from 2 μm to 50μm, with from 3 μm to 35 μm being more typical and is not oriented.

Multilayer film structures typically include ≧one layer formed from apolymer other than that used in the barrier film layer. Selection ofsuch polymer(s) depends upon intended end uses for the multilayerstructure. If freedom from chlorine is essential, all layers preferablylack chlorine. In applications where some chlorine is acceptable, suchas packaging, protective clothing or soil fumigation, the multilayerfilm structures may also comprise chlorinated film layers in addition tothe essentially amorphous, non-chlorinated polymeric barrier film of thepresent invention.

Polymers suitable for use in forming non-barrier layers include: LDPE,linear low density polyethylenes (LLDPE), ultra low density polyethylene(ULDPE), homogeneous EAO copolymers, HDPE, PP homo- or copolymers,rubber modified PP, low modulus PP homo- or copolymers, lowcrystallinity PP homo- or copolymers, syndiotactic PP homo- orcopolymers, ethylene-propylene-diene monomer elastomer (EPDM),ethylene-polypropylene rubbers (EPF), substantially linear EAOcopolymers, styrene-butadiene copolymers (SB or SBS), SEBS copolymers,styrene-isoprene copolymers (SI or SIS), ethylene-alkyl acrylatecopolymers, such as, for example, ethylene-methyl acrylate (EMA),ethylene-butyl acrylate (EBA), ethylene-ethyl acrylate (EEA),ethylene-vinyl acetate (EVA), ethylene-acrylic acid copolymers (EAA),ionomer resins, elastomeric co-polyesters, ethylene-methyl acrylic acidcopolymers (EMAA), polynorbornene, ESI, thermoplastic polyurethane(TPU), polyether-amide block copolymers, EVA-carbon monoxide copolymers(EVACO), MAH-modified polyethylene, maleic anhydride modified EVA,MAH-EMA, MAH-EBA, MAH-PP, glycidyl methacrylate modified EMA, glycidylmethacrylate modified EBA, glycidyl methacrylate modified EVA,polyamides, and blends thereof. One such blend includes an amorphous EAOpolymer and a low crystallinity PP homo- or copolymer. EP 641,647 andits US equivalent U.S. Pat. No. 5,616,420 as well as EP 527 589, therelevant teachings of which are incorporated herein by reference,disclose, in part, blends of an amorphous polyolefin and a crystallinePP.

The use of copolymers of olefins and polar comonomers will additionallyimprove the high frequency (HF) sealing properties of the film.

Chlorinated polymers which can optionally be used together with theessentially amorphous, non-chlorine containing barrier films of thepresent invention include, for example, polyvinyl chloride (PVC),chlorinated polyethylene (CPE), poly(vinylidene chloride) (PVDC),PVDC/VC copolymers (PVDC/VC), PVDC/methyl acrylate copolymers (PVDC/MA),and mixtures thereof.

In a multilayer structure, the polymeric layers located immediatelyadjacent to the barrier layer will typically function as adhesive or tielayers, while other, non-adjacent layers typically function asintermediate or skin layers. The overall thickness of such a multilayerfilm structure depends upon the individual film or layer thicknesses. Anindividual film thickness depends upon a variety of factors, such asease and cost of manufacturing a film of a given thickness, filmphysical and chemical properties, and the environment to which themultilayer film structure will be exposed. The overall thickness of sucha multilayer film structure typically ranges from 20 μm to 350 μm, withfrom 30 μm to 200 μm being more typical, and from 40 μm to 150 μm beingmost typical.

When used in a TDDS application, such as a backing layer for a TDDSarticle or patch, the multilayer film structures typically have a two orthree layer configuration with an overall thickness of 15 to 80 μm,preferably 25 to 50 μm. Such structures typically have an A/B or anA/C/D configuration. Layer A serves as a barrier layer and desirablycomprises PET-G, APE-1, a blend of PET-G and APE-1, an amorphousthermoplastic polyester homo- or copolymer resin that has a Tg of atleast 50° C., and blends thereof such as a blend of one or both of PET-Gand APE-1 with such a resin. Layer A has a thickness of 8-20 μm,preferably 8-15 μm. Layer B comprises an EVA copolymer with a vinylacetate content of 15-30 wt %, an EMA copolymer with a methyl acrylatecontent of 15-30 wt % or an EBA copolymer with a butyl acrylate contentof 15-30 wt %. Layer C includes all of the copolymers of Layer B plusMAH-g-EVA, MAH-g-EMA, MAH-g-EBA, glycidyl methacrylate grafted EVA, EMAor EBA, ethylene-acrylic ester-MAH terpolymers, ethylene-acrylicester-glycidyl methacrylate terpolymers, ethylene-glycidyl methacrylatecopolymers, SB copolymers, EVACO terpolymers, SI and SIS polymers, andblends thereof, together with. Layer C functions as a tie layer and hasa thickness of 2-15 μm. Layer D comprises any of the polymers identifiedabove as suitable polymers for use in forming non-barrier layers otherthan the polyamides. The EVA, EBA and EMA, when used, preferably have anon-ethylene monomer content of 6-20 wt %. Any or all of layers B, C andD may include one or more of the slip and antiblock additives disclosedherein. In addition, any one or more of layers A-D may include anadditive such as an antioxidant, a pigment, a ultraviolet lightstabilizer or a processing aid. As with the other multilayer filmstructures, surface layer treatments may enhance one or more features ofthose structures having utility in TDDS applications.

Unless otherwise stated, as in the case of <50, each range includes bothendpoints that establish the range.

Conventional processes such as blowing or casting, co-extrusion,extrusion coating, extrusion lamination, or adhesive lamination mayprepare the multilayer film structures of the present invention.

When used in a monolayer or a multilayer film structure as a barrier tomolecules having a diameter≧0.40 nm, the barrier films of the inventionhave a 3-methyl indole breakthrough time ≧2 hours (hrs), preferably2-300 hrs, and a DEDS breakthrough time ≧8 minutes (min), preferably20-1200 min. Such film structures serve as useful barriers to odors andorganic molecules.

Table 1 provides representative barrier films useful in accordance withthe present invention along with their respective 3-methyl indole andDEDS breakthrough times. Table 1 and succeeding Tables 2-4 are intendedto be illustrative only and do not limit scope of the present inventionin any way.

TABLE 1 3-Methyl Indole Breakthrough Time (hrs)² DEDS Breakthrough time(min) 2 Film 2 4 10 20 40 80 150 200 300 8 20 50 100 150 300 500 10001200 SAN Y Y Y Y Y Y Y Y N Y Y Y Y N N N N N SAN-ESI Y Y Y Y Y Y Y N N YY Y Y N N N N N ABS Y Y Y Y Y Y N N N Y Y Y Y Y N N N N PMMA Y Y Y Y Y YY Y Y Y Y Y N N N N N N PMMA-IM¹ Y Y Y Y Y Y Y N N Y Y Y N N N N N N PCY Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y PC-IM¹ Y Y Y Y Y Y Y Y N Y Y Y Y Y YY N N PC-ABS Y Y Y Y Y Y Y N N Y Y Y Y Y Y Y Y N PET-G Y Y Y Y Y Y Y Y YY Y Y Y Y Y N N N PET-G/SB Y Y Y Y Y Y Y Y Y Y Y Y Y N N N N N PET-G/SBSY Y Y Y Y Y Y N N Y Y Y N N N N N N GPPS/SB Y Y N N N N N N N Y Y N N NN N N N GPPS/ESI Y Y Y Y Y Y Y Y N Y Y Y Y Y N N N N GPPS/SIS Y N N N NN N N N Y N N N N N N N N APE-1/PET-G Y Y Y Y Y Y N N N Y Y Y Y Y N N NN (50/50%) ¹IM = Impact modified; ²all time entries are > time stated; Ymeans breakthrough time exceeds time stated; N means breakthrough occursbelow time stated

When used in a monolayer or a multilayer film structure as a barrier tomolecules having a diameter≧to 0.40 nm, the barrier films of theinvention have a 3-methyl indole breakthrough time ≧2 hrs, preferably2-300 hrs, and an H₂S breakthrough time ≧40 seconds (secs), preferably40-250 secs. Such films serve as useful barriers to odors and organicmolecules. Table 2 provides representative barrier films useful inaccordance with the present invention along with their respective3-methyl indole and H₂S breakthrough times, wherein the films may bemonolayer films or components in a multilayer film structure.

TABLE 2 3-Methyl Indole Breakthrough Time (hrs)² H₂S Breakthrough Time(secs)² 2 4 10 20 80 150 200 300 40 100 150 200 250 400 >600 SAN Y Y Y YY Y Y N Y Y Y N N N N ABS Y Y Y Y Y N N N Y N N N N N N PMMA Y Y Y Y Y YY Y Y Y Y Y Y N N PC Y Y Y Y Y Y Y Y Y N N N N N N PC-IM¹ Y Y Y Y Y Y YN Y N N N N N N PET-G Y Y Y Y Y Y Y Y Y Y Y Y Y Y N APE-1/PET-G Y Y Y YY N N N Y Y Y Y Y Y Y (50/50%) ¹IM = Impact modified; ²all time entriesare > time stated; Y means breakthrough time exceeds time stated; Nmeans breakthrough occurs below time stated

Yet, when used in a monolayer or a multilayer film structure as abarrier to molecules having a diameter≧0.40 nm, the barrier films of theinvention have a DEDS breakthrough time of 8 minutes (min), preferably8-1200 min, and an H₂S breakthrough time of 40 secs, preferably 40-250secs. Such films serve as useful barriers to odors and organicmolecules. Table 3 provides representative barrier films useful inaccordance with the present invention along with their respective DEDSand an H₂S breakthrough times, wherein the films may be monolayer filmsor components in a multilayer film structure.

TABLE 3 DEDS Breakthrough Time (min)² H₂S Breakthrough Time (secs)² 8 2050 100 150 300 500 1000 1200 40 100 150 200 250 400 >600 SAN Y Y Y Y N NN N N Y Y Y N N N N ABS Y Y Y Y N N N N N Y N N N N N N PMMA Y Y Y N N NN N N Y Y Y Y Y N N PC Y Y Y Y Y Y Y Y Y Y N N N N N N PC-IM¹ Y Y Y Y YY Y N N Y N N N N N N PET-G Y Y Y Y Y Y N N N Y Y Y Y Y Y N APE-1/PET-GY Y Y Y Y N N N N Y Y Y Y Y Y Y (50/50%) ¹IM = Impact modified; ²alltime entries are > time stated; Y means breakthrough time exceeds timestated; N means breakthrough occurs below time stated

Moreover, when used in a monolayer or a multilayer film structure as abarrier to odors, the barrier films have a 3-methyl indole breakthroughtime ≧2 hrs, preferably 2-300 hrs, a DEDS breakthrough time ≧8 min,preferably 8-1200 min, and an H₂S breakthrough time ≧40 secs, preferably40-250 secs.

Table 4 provides representative barrier films useful in accordance withthe present invention along with their respective 3-methyl indole, DEDSand an H₂S break through times, wherein the barrier films may bemonolayer films or components in a multilayer film structure.

TABLE 4 3-Methyl Indole Breakthrough Time (hrs)² DEDS Breakthrough time(min)² 2 4 10 20 40 80 150 200 300 8 20 50 100 150 300 500 1000 1200 SANY Y Y Y Y Y Y Y N Y Y Y Y N N N N N ABS Y Y Y Y Y Y N N N Y Y Y Y Y N NN N PMMA Y Y Y Y Y Y Y Y Y Y Y Y N N N N N N PC Y Y Y Y Y Y Y Y Y Y Y YY Y Y Y Y Y PC-IM¹ Y Y Y Y Y Y Y Y N Y Y Y Y Y Y Y N N PET-G Y Y Y Y Y YY Y Y Y Y Y Y Y Y N N N APE/PET-G Y Y Y Y Y Y N N N Y Y Y Y Y N N N N(50/50%) H₂S Breakthrough Time (secs)² 40 100 150 200 250 400 >600 SAN YY Y N N N N ABS Y N N N N N N PMMA Y Y Y Y Y N N PC Y N N N N N N PC-IM¹Y N N N N N N PET-G Y Y Y Y Y Y N APE/PET-G Y Y Y Y Y Y Y (50/50%) ¹IM =Impact modified; ²all time entries are > time stated; Y meansbreakthrough time exceeds time stated; N means breakthrough occurs belowtime stated

In addition, depending upon the end-use of the polymeric barrier filmsof the present invention, it may be desirable that the polymeric barrierfilms of the present invention or multilayer polymeric film structurehaving a polymeric barrier film of the present invention as a componentfilm exhibit additional properties.

For example, in addition to barrier properties, it is often desirablethat polymeric films not emit noise when crumpled. In ostomy orincontinence applications, it is desirable that the ostomy orincontinence bags not emit noise. However, when crumpled, most polymericfilms, especially multilayer polymer films comprised of individualpolymeric film layers having different rigidities (i.e., modulus), emitnoise. When a reduction in noise is desired, a “noise dampening” polymermay be blended, typically in amounts ≧25 wt %, with other (second)polymeric resins to form polymeric films of the present invention havingbarrier properties. Typically, these polymeric barrier films have anoise level ≦50 decibels (dBA) at one or more octave frequency bandsbetween 1 kilohertz (kHz) and 16 kHz.

In addition, these polymeric resins having quietness properties may beincluded as component films in multilayer film structures to formmultilayer film structures of the present invention having quietnessproperties. Typically, the noise dampening polymer will be present at≧30 wt % in the layer and represent ≧25 wt % of the total filmcomposition. Alternatively, a quiet polymeric film may be formedentirely from a noise-dampening polymer and included as a component filmin a multilayer film structure of the present invention having quietnessproperties.

A quiet film according to the present invention will typically be usedas a skin or an adhesive layer, but could also be used as an internallayer.

Typically, a noise dampening polymer will have a Tan Δ value ≧0.25 at atemperature within the range between −5° C. and 15° C. or ≧0.32 in thetemperature range of from −12° C. to −5° C. Typical noise dampeningpolymers include, but are not limited to, polynorbornene polymers, lowcrystallinity PP homo- or copolymers having a heat of fusion <50Joules/gram (J/g), or syndiotactic PP homo- or copolymers, or atacticPP, or ESI resins. TPUs, EVA copolymers, EMA copolymers, EBA copolymers,PVC, and CPE are not within the scope of this invention with regard touse as noise dampening polymers.

The heat of fusion is determined by differential scanning calorimetry(D.S.C.). The equipment is calibrated using an indium standard. The heatof fusion of PP is determined using a heating rate of +10° C./minutefrom −50° C. to +220° C. The heat of fusion is integrated between +25°C. and +180° C.

The noise dampening polymer can also be a polymeric composition obtainedby blending a polymer which does not have a Tan Δ value ≧0.25 at atemperature within the range between −5 and 15° C. or ≧0.32 at atemperature within the range between −12° C. and −5° C. with at leastone of a compatible resin, plasticizer or tackifier that modifies itsTan Δ to such a value. One such blend is the blend of amorphous EAOpolymer and a low crystallinity PP. homo- or copolymer noted above.

Examples of such Tan Δ modifications by blending are described in: TheViscoelastic Properties of Rubber Resin Blends: Parts I., II. and III.,J. B. Class and S. G. Chu, Journal of Applied Polymer Science, Vol. 30,805-842 (1985). Light and Stable Resins for Hot-melt Adhesives, P.Dunckley, Adhesives Age, November 1993. A Statistical Approach toFormulating Deep Freeze HMAS, W. J. HONIBALL, J. LEBEZ and al.,Adhesives Ages, May 1997, pages 18-26. Tackifier Resins, James A.Schlademan, Handbook of Pressure Sensitive Adhesive Technology, Chapter20, pages 527-544.

While certain polymers, such as the PP homopolymer and propylenecopolymers (PCP-1, PCP-2 and PCP-3) shown in Table 5 below, may providesufficient noise dampening performance to serve as a sole noisedampening polymer, others require augmentation with at least one otherpolymer or polymer modifier. In addition, blends of two or more resinsserve as effective substitutes for such “sole noise dampening polymers”.For example, a blend of an amorphous poly (α-olefin) such as REXTAC®APAO2180, and a 2 melt flow rate random propylene/ethylene copolymer(2.3 wt % ethylene)) approximates one or more of the REXFLEX® flexiblepolyolefins (FPOs) shown in Table 5. Other blends of a high molecularweight (low melt flow rate) amorphous poly (α-olefin) and a randompropylene copolymer also provide effective results. One such blend ismarketed by Ube Industries under the trade designation CAP-350. EP527,589 and its US equivalent U.S. Pat. No. 5,468,807, and EP 641,647and its US equivalent U.S. Pat. No. 5,616,420, the relevant teachings ofwhich are incorporated herein, disclose such blends in an intermediatelayer.

In addition, the use of a noise-dampening polymer or polymer compositionis especially advantageous when it is included in a multilayer filmstructure that contains ≧one other polymeric film layer which has astorage modulus (G′) ≧2×10⁴ Newtons per square centimeter (N/cm² ) atroom temperature. The polymeric film layers which have a storage modulus(G′) ≧2×10⁴ N/cm² are typically prepared from amorphous thermoplasticpolyesters, such as PET-G, polyethylene terephthalate (PET),polybutylene terephthalate (PBT), and other thermoplastic polyesters,EVOH, PC, polyvinyl alcohol (PVA), SAN, ABS, PMMA, SB copolymers,polyacrylonitrile, polyamides and co-polyamides, such as PA-6, PA-6,6,PA-11, and PA-12, amorphous polyamides, MXD6 polyamide, PVDC, PVDC/VCcopolymers, PVDC/MA copolymers, polyhydroxy amino ether copolymers(PHAE), polyurethanes, epoxies, polyethylene naphthalate (PEN),syndiotactic polystyrene, and polystyrene.

Preferred commercially available amorphous thermoplastic polyestersinclude EASTART™ PETG copolyester 6763 (Eastman Chemical, 1.27 g/cm³density (ASTM D1505), and 10 cm³-mm/m²-24 hr-atmosphere oxygenpermeability (ASTM D3985)) and Mitsui B-100 (Mitsui Chemicals Inc., 1.35g/cm3 density, Tg of 62° C.). The amorphous thermoplastic polyesters maybe used singly or blended together. Using the PETG and B-100 resins byway of example, the blends desirably include from 0 to 100 wt % B-100and conversely from 100 to 0 wt % PETG. Preferred blends include from 10to 80 wt % B-100 and 90-20 wt % PETG. More preferred blends include 20to 70 wt % B-100 and 80-30 wt % PETG. In all instances, the combinedresins total 100 wt % and all percentages are based on blend weight.B-100 resin is an amorphous thermoplastic co-polyester resin supplied byMitsui Chemicals Europe GmbH, it holds the chemical abstracts reference87365-98-8. This is a copolymer of isophthalic acid (42˜48 mole %),terephthalic acid (2˜8 mole %), ethylene glycol (>40 mole % ) and1.3-bis (2-hydroxyethoxy)benzene (<10 mole %). The resin has a glasstransition temperature of 62° C. and a density of 1.35.

Typically, when the noise dampening polymer or polymer composition isused as part of a multilayer polymeric film structure, it may be presentas any of the layers of the multilayer film structure although it ispreferred to have it included in a skin layer or in a layer close to anoutside surface of the structure.

Although described above in connection with polymeric films havingbarrier properties, it is understood that the polymeric films havingnoise dampening characteristics may also be useful in other applicationswhere barrier properties are not required. Thus, another aspect of thepresent invention is the use of polymers or polymer compositions havinga Tan Δ value ≧0.25 at a temperature within the range between −5° C. and15° C. or ≧0.32 at a temperature within the range of from −12° C. to −5°C. as noise dampening polymeric films or quiet polymeric films.

Further, it may be desirable for the end use application to seal some ofthe multilayer films described previously, for example, to produce bags.In some instances, the seal strength of some skin polymer compositionsmay be too low when the film is sealed to itself or to other polymers. Ahigher seal strength may be obtained by adding a sealant layer as theoutermost layer in the film, or by blending into the outermost layer ofthe film a polymer that improves the seal strength.

EXPERIMENTAL SECTION I. Barrier Properties

The following developed analytical test methods help quantify barrierproperties of the polymeric films of the present invention to oxygen,hydrogen sulfide (H₂S) gas, organic sulfides and indoles. DEDS serves asa model organic sulfide compound and 3-methyl indole functions as amodel indole compound. Whenever technically possible, permeation testingoccurs in high humidity conditions and at 40° C. to more closelysimulate the conditions encountered by an ostomy bag in use (i.e.,approximating an ostomy bag warmed by body heat and subject to thehumidity which exists between human skin and clothing).

The barrier properties of the films to H₂S gas, DEDS and 3-methyl indoleare expressed in terms of breakthrough time (B.T.) and/or permeationrate (P.R.). The breakthrough time (B.T.) or time lag, is proportionalto the square of the thickness of the barrier resin (See PolymerPermeability, pages 11-74, J. Comyn, Elsevier Applied Science Publishers(1985):

B.T.=T²/60D,

Wherein: B.T.=breakthrough time (hrs); T=thickness of film (cm); andD=diffusion coefficient of the permeant in the resin (cm²/sec).

The same reference teaches that permeation rate (P.R) is inverselyproportional to the thickness of the barrier resin:

P.R.=P/T,

wherein P=resin permeability; and T=thickness of film (cm).

The B.T. represents short-term barrier properties of a product, i.e.,before the permeated quantity is high enough to reach the odor thresholdof the permeant if the detection is made by the human nose. The B.T. canrange from seconds to months depending on the products. The P.R. is morerepresentative of the long-term barrier properties of a product.

The resins used for fabricating the films described in the followingexamples are listed in Table 5.

TABLE 5 Melt Index Resin Name Type Supplier Density (g/10 min) OtherAFFINITY* INSITE* The Dow 0.902  1.0¹ low crystallinity PL 1880technology Chemical Co. homogeneous copolymer polymer of ethylene andalpha- (ITP-1) olefin AFFINITY* INSITE* The Dow 0.875  3.0¹ lowcrystallinity KC 8852 technology Chemical Co. homogeneous copolymerpolymer of ethylene and alpha-olefin (ITP-2) AFFINITY* INSITE* The Dow0.870  1.0¹ low crystallinity EG 8100 technology Chemical Co.homogeneous copolymer polymer of ethylene and alpha-olefin (ITP-3)ATTANE* ULDPE-1 The Dow 0.912  1.0¹ copolymer of ethylene 4201 ChemicalCo. and octene ATTANE* ULDPE-2 The Dow 0.913  3.2¹ copolymer of ethylene4202 Chemical Co. and octene ATTANE* ULDPE-3 The Dow 0.905  0.8¹copolymer of ethylene 4203 Chemical Co. and octene AFFINITY* ITP-4 TheDow 0.896  1.6¹ low crystallinity PF 1140 Chemical Co. homogeneouscopolymer of ethylene and alpha-olefin CN 4420 slip and Southwest — — 4%erucylamide + 4% antiblock Chemical stearamide + 20% silica masterbatchin EVA carrier (ADD-1) REXFLEX ® homopolymer Huntsman 0.88 14⁸ lowcrystallinity and FPO WL101 polypropylene low modulus PP, (heat (PP)fusion ˜25 J/g) REXFLEX ® copolymer Huntsman 0.88  2.8⁸ lowcrystallinity and FPO WL201 polypropylene low modulus PP (heat of(PCP-1) fusion ˜20 J/g) REXFLEX ® copolymer Huntsman 0.88  6⁸ lowcrystallinity and FPO WL210 polypropylene low modulus PP (heat of(PCP-2) fusion ˜20 J/g) REXFLEX ® copolymer Huntsman 0.88 19⁸ lowcrystallinity and FPO WL203 polypropylene low modulus PP (heat (PCP-3)fusion ˜20 J/g) VISTAFLEX ™ non-crosslinked Advanced 0.91 — — 671Npolypropylene/ Elastomer ethylene- Systems propylene-diene monomer(PP-EPDM) GRIVORY ™ amorphous EMS Chemie 1.18 — Tg = 125° C. G21co-polyamide A.G. (co-PA-1) GRILON ™ polyamide 6 EMS Chemie 1.14 — F34(PA6) A.G. EVAL EP ethylene vinyl Kuraray 1.19  5.5¹ 44 mol % ethyleneE105 alcohol (EVOH) GRILON ™ co-polyamide EMS Chemie 1.20 — Tg = 96° C.BMFE 4581 (co-PA-2) A.G. GRILON ™ polyamide 6-12 EMS Chemie 1.10 — meltpoint = 200° C. CR9 (PA 6-12) A.G. STYRON* GPPS-1 The Dow 1.05  2.5² 637Chemical Co. STYRON* GPPS-2 The Dow 1.05  2.5² 686 Chemical Co. STYRON*GPPS-3 The Dow 1.05  1.5² 665 Chemical Co. STYRON* high impact The Dow1.05  4.5² 8.5% rubber 5192 polystyrene Chemical Co. (HIPS-1) STYRON*HIPS-2 The Dow 1.05  3.0² 7.2% rubber 492U Chemical Co. PET biaxiallyoriented MICEL, France — — 12 microns thick polyethylene monolayer filmterephthalate film, thermal class B (130° C.) medium haze H (PET) B-100amorphous Mitsui 1.35 Tg of 62° C. thermoplastic Chemicals co-polyesterEurope resin (APE-1) GmbH EASTAR ™ PET-G Eastman 1.27 Inherent1,4-benzenedicarboxylic 6763 Chemical Viscosity = acid, dimethyl ester,0.75 polymer with 1,4-cyclohexane-dimethanol and 1,2-ethanediol.Amorphous polyester. FINACLEAR ™ SBS block Fina 1.01  7.5² 70 wt %styrene 520 copolymer (SBS) V920 PMMA Atohaas 1.18  8³ HFI-7 impactmodified Atohaas 1.17 11³ polymethyl- methacrylate (PMMA-IM) CALIBRE*PC-1 The Dow — 20⁴ 0201-20 Chemical Co. CALIBRE* PC-2 The Dow — 20⁴ 200Chemical Co. CALIBRE* PC-3 The Dow — 22⁴ 201-22 Chemical Co. CALIBRE*impact-modified The Dow — 11⁴ IM 401.11 polycarbonate Chemical Co.(PC-IM-1) PULSE* 830 PC-ABS The Dow —  2.5³ terpolymer alloy ChemicalCo. K-RESIN SB Philipps 1.01  8.0² KR01 Petroleum Chemicals INDEX* DSESI The Dow —  1.0¹ 69 wt % styrene 201.00 Chemical Co. TYRIL* 790 SAN-1The Dow —  9.0³ 29 wt % acrylonitrile Chemical Co. TYRIL* 100 SAN-2 TheDow —  8.0³ 25% acrylonitrile Chemical Co. MAGNUM* ABS The Dow —  2.8³25% acrylonitrile, 340 Chemical Co. 12% rubber ELVAX ® EVA copolymerDuPont 0.94  0.7 18 wt % V.A. 3165 (EVA-1) ELVAX ® EVA copolymer DuPont0.94  8¹ 18 wt % V.A. 3174 (EVA-2) ELVAX ® EVA copolymer DuPont 0.94  2¹25 wt % V.A. 3190 (EVA-3) ESCORENE ™ EVA copolymer EXXON —  5.5¹ 24.5%wt % V.A. 740.16 (EVA-4) BYNEL ® MAH-g-EVA DuPont —  7.7¹ adhesive resin21E533 copolymer (MAH-g-EVA-1) BYNEL ® MAH-g-EVA-2 DuPont —  5.7¹adhesive resin 3860 VECTOR ® SIS-1 Dexco — 40² 44% styrene 4411 VECTOR ®SIS-2 Dexco 13² 30% styrene 4211 LOTRYL ™ 24 EMA Atochem —  0.5¹ 24 wt %M.A. MA 005 OREVAC ™ MAH-g-EMA Atochem  3.5¹ ˜28% maleic anhydride 18613LOTADER ™ ethylene-methyl Atochem —  6¹ GMA AX 8900 acrylate-glycidylmethacrylate (EMAGMA) LDPE 320 LDPE-1 The Dow 0.924  1.75¹ Chemical Co.LDPE 501 LDPE-2 The Dow 0.922  1.9¹ Chemical Co. SARAN 469 PVDC The Dow— — 80/20 wt % VDC/vinyl Chemical Co. chloride copolymer ADMER ™ NFMAH-g-PE Mitsui & Co. —  4.0 adhesive resin 530 KRATON ™ FG MAH-g-SEBSShell 0.91 21.0⁶ 28 wt % styrene, 1901 X Chemicals 2 wt % maleicanhydride CPE/EVA blend of 60% — — — — blend chlorinated polyethylene(36 wt % chlorine, .2% residual crystallinity) and 40% EVA (15 wt %vinyl-acetate, melt index of 2.5 @ 190/2.16). EVA EVA — — 0.5 to 5.0 15to 25 wt % vinyl acetate HDPE any type of HDPE — 0.955 to 0.965 0.2 to8.0¹ — film grade EEA ethylene - — — 0.5 to 5¹ 15 to 25 wt % ethylacrylate ethyl acrylate EMA ethylene methyl- — — 0.5 to 5.0 15 to 25 wt% methyl acrylate acrylate XU73109.01 PC-4 The Dow — 12.5⁵ — ChemicalCompany Xu 73114.03 PC-IM-2 The Dow —  8.5⁴ — Chemical Company LDPE anytype of — 0.917 to 0.925 0.5 to 8.01 — LDPE film grade EAA ethyleneacrylic The Dow — 1.0 to 15.0 5 to 10 wt % acrylic acid acid copolymerChemical Company CN 706 slip additive Southwest — — 10% stearamide inEVA resin concentrate Chemical (ADD-2) 100371 antiblock Ampacet — — 20%silica in polyolefin concentrate (ADD-3) 100501 slip antiblock Ampacet —— 15% silica + 5% concentrate erucamide in polyolefin (ADD-4) *Trademarkof The Dow Chemical Company ¹As determined by ASTM D-1238 at 190°C./2.16 kg ²As determined by ASTM D-1238 at 200° C./5 kg ³As determinedby ASTM D-1238 at 230° C./3.8 kg ⁴As determined by ASTM D-1238 at 300°C./1.2 kg ⁵As determined by ASTM D-1238 at 250° C./1.2 kg ⁶As determinedby ASTM D1238 at 230° C./5 kg ⁷As determined by ASTM D1238 at 224°C./1.2 kg ⁸As determined by ASTM D1238 at 230° C./2.16 kg

TEST 1 Determination of the Odor Breakthrough Time of Polymer Films to3-Methyl Indole

The method for determining 3-methyl indole breakthrough time is anolfactometric method, similar to the odor transmission test forcolostomy bag material described in Appendix G of the British StandardBS 7127, part 101 (1991).

Preliminary Remarks:

3-Methyl indole (skatole) has a very low odor threshold concentration.Values of 0.02 parts per million (ppm) down to 0.0003 parts per billion(ppb) odor threshold detection level in air are reported in theliterature. The test must be performed with a test panel of a minimum of3 people, with 5 testers being ideal.

Objective and Principle:

The objective of this test method is to determine the odor breakthroughtime of 3-methyl indole through polymer films. A polymer film is formedinto a small pouch, filled with a 3-methyl indole solution, and sealed.Water and the sealed polymeric pouch are placed within a glass bottleand the bottle closed. The bottle is opened at different time intervals,sniffed by a test panel and compared to a reference. The breakthroughtime is defined as the time when the average number of testers detectsthe 3-methyl indole odor in the test bottle.

Equipment

sealing equipment, e.g. household heat sealer for freezer bags

1 cm³ automatic pipette

1-liter, wide-mouth bottle with glass stoppers (46/60 mm)

clear glass beads, diameter of approx. 10 mm.

distilled or deionized water

laboratory oven regulated at 40° C.±1° C.

A. Preparation of the 3-Methyl Indole Test Solution

3-Methyl indole is almost insoluble in water (0.005 wt % at 20° C.).Prepare the 3-methyl indole solution for the test by dissolving 0.25grams (g) of.3-methyl indole crystals in 10 milliliters (mL) of ethanol,and then adding 100 mL of distilled water. The resultant solution has aconcentration of 2.27 grams per liter (g/L) of 3-methyl indole.

B. Test Procedure

1. Cut a piece of polymer film of dimensions of approx. 220 mm × 120 mm,fold it lengthwise and seal two sides to make a pouch. 2. Carefully fillthe pouch with 1 mL of the 3-methyl indole solution using the pipette,ensuring that no 3-methyl indole solution is dripped onto the seal areaor on the outside of the film. Seal the pouch. The dimensions of thefinished pouch within the sealed area are 100 mm × 100 mm. 3. About 1hour in advance of testing, prepare a pouch from a film having a verylow barrier to 3-methyl indole (e.g., a 15 μm to 40 μm thick LDPE orHDPE film), using the procedures of 1 and 2 above. Fill the pouch with 1mL of the 3-methyl indole solution. This pouch shall be used as thereference odor rating value of 5. 4. Prepare a pouch from the film to betested, or with a film having no marked odor of its own (e.g.,polyethylene) and fill with 1 mL of a water/ethanol mixture (10/1solution). This pouch shall be used as the reference odor rating valueof 1. 5. Fill the glass bottles with 2 layers of glass beads. Add somewater, but do not submerge the glass beads. 6. Place a sealed pouch ineach glass bottles. Put some grease on the glass stopper, close thebottles, and place them in an oven at 40° C. 7. At defined intervals,take the bottles out of the oven and let the individual members of thetest panel evaluate the smell in each bottle. Give the smell a relativerating values from 1 to 5, 1 being no smell or neutral/polymeric odor(reference film with water), 2 being 3-methyl indole odor very low butdetected, and 5 being very odorous (reference film with 3-methyl indolesolution). The time interval is dependent on the breakthrough time ofthe film, e.g., 1 to 4 hours for short times, and up to 1-4 days forlong times. Calculate the average odor rating of the film. 8. Continuethe test until the average odor rating of the film is ≧ 2. 9. For eachfilm, plot the odor rating (arithmetic average of all testers) versustime. The breakthrough time is defined as the time required to reach anaverage odor rating of 2. This value is obtained by linearinterpolation.

More than one sample can be tested at the same time, but it is notrecommended to go above 6 or 7 at a time. All testers can smell the samebottles, but care must be taken to let these open the shortest possibletime. The same bottles can also be used for the different testing times.It is important to smell the different bottles in the order ofincreasing odor rating. Smelling a very odorous bottle (like the onewith the film rated 5) at the beginning of a series tends toanaesthetize/saturate the sense of smell and can lead to lower odorratings. The bottle with the odor reference 5 must be sniffed only atthe end of a series and last. The odor rating is the arithmetic averageof the ratings of the different testers. If range values greater than 2within the individual data are found, look closely for an outlier andeliminate it from the calculation whenever possible.

TEST 2 Oxygen Permeability of Polymeric Films

Measure oxygen permeability of the films using an OX-TRAN 10-50 oxygenpermeability tester available from Modern Controls Inc. (Minneapolis,Minn., USA) using the ASTM 3985-81 test method at 23° C., and 65-70%relative humidity.

Table 6 shows the oxygen permeability and the 3-methyl indolebreakthrough times of a series of polymeric films. The films inComparative Examples (Comp Ex) number A-F are currently used in ostomybag applications. The films of the various Examples (Ex) designated withan Arabic numeral represent the present invention. Comp Ex M is a plainpolyethylene (PE) film and has the shortest 3-methyl indole breakthroughtime of all examples, since PE has very little barrier properties to3-methyl indole, this film was used as the odor reference 5 in the3-methyl indole breakthrough time test method. The other examples havehigher breakthrough times due to the presence of a “barrier resin” intheir structure. The resins used for the fabrication of these films arelisted in Table 5.

TABLE 6 Barrier Total Ex or Layer Film Oxygen 3-Methyl Comp. ThicknessThickness Permeability Indole B.T. Ex. Film Description Barrier Layer(μm) (μm) (cm3/m2 · day · atm) (hours) A LDPE/EVA/PVDC/EVA/LDPE PVDC 5.5¹ 70 13 7 B LDPE/EVA/PVDC/EVA/LDPE PVDC 10.1² 75 4.5 24 CCPE/EVA/PVDC/EVA PVDC  9.1³ 100 6 65 D CPE/EVA/PVDC/EVA PVDC 10 75 7.550 E EVA/MAH-g-EVA-2/co-PA- amorphous  6.2⁴ 70 42 20 1/MAH-g-EVA-2/EVAco-PA F EVA/MAH-g-EVA-2/co-PA- amorphous 10.2⁵ 70 30 >501/MAH-G-EVA-2/EVA co-PA G EVA/MAH-g-PE/EVOH/MAH- EVOH  7 60 14 1/4.5⁶g-PE/EVA H LDPE/5 μm adhesive/PA6 PA6 18 70 41 <2 I 50 μm LDPE/10 μm PA6-12 25 85 76 <2 adhesive/PA6-12 J LDPE-1/MAH-g-EVA-2/co-PA-2 co-PA  5.293 6.9 3 4581/MAH-g-EVA-2/LDPE-1 1 LDPE-10/EVA/50:50 50/50 blend 10 1001625 85 GPPS-1 and HIPS-1/ of GPPS and EVA/LDPE-1 HIPS 2LDPE/MAH-g-EVA-2/SAN-2/ SAN 35 85 1360 200 MAH-g-EVA-2/LDPE 3LDPE/MAH-g-EVA-2/PMMA/ PMMA 35 85 138 390 MAH-g-EVA-2/LDPE 4 50:50GPPS-2 and 50/50 blend 19 19 >2000 >1490 HIPS-2⁷ of GPPS/HIPS K LDPEcoated with 10 μm cationic 10 100 44 1 cationic epoxy epoxy resinlacquer⁸ L coextruded film with polyhydroxy-  4.5 24 72 <1 EAA skins and4.5 μm aminoether polyhydroxyamino- ether resin M HDPE (Reference Film —15 >2000 <0.3 with odor rating = 5) 5 PETG PET-G 18 18 390 >388 6LDPE/EVA/ABS/EVA/LDPE ABS  6 75 2260 −85 7 LDPE/EVA/75:25 PET-G and75:25 blend  7.3¹¹ 80 712 160 SBS/EVA/LDPE of PET-G and SBS 8 LDPE501/MAH-g-EVA-2/ PMMA  5 75 665 >175 V920/MAH-g-EVA-2/LDPE 9LDPE-2/MAH-g-EVA-2/PMMA- impact- 10 75 607 175 IM/MAH-g-EVA-2/LDPE-2modified PMMA 10 LDPE-2/EEA/PC/EEA/ PC¹³  9.0¹⁴ 75 1740 >147 LDPE-2¹² 11LDPE-2/MAH-g-ETA-2/PC-IM- impact  5.7¹⁶ 75 2375 ˜2702/MAH-g-EVA-2/LDPE-2¹⁵ modified PC 12 LDPE-2/EVA/PC-ABS/EEA/ PC/ABSalloy  3.0 75 4390 185 LDPE-2 13 LDPE-2/EVA/70:30 PET-G and 70:30 blend10 75 962 >147 SB/EVA/LDPE-2 of PET-G and SS N PET¹⁷ PET 13 13 141 17514 LDPE-2/EVA/70:30 GPPS-3 and 70:30 blend 10 75 3865 4 SB/EVA/LDPE-2 ofGPPS and SB 15 LDPE-2/EVA/PC-1/EMA/ PC  7.4 75 1995 −315 LDPE-2¹⁸ 16LDPE-2/EVA/85:15 PET-G and 85:15 blend  4.5²⁰ 75 1070 >147SB/EVA/LDPE-2¹⁹ of PET-G and SB ¹represents an average between 4.0 μmand 7.1 μm ²represents an average between 10.0 μm and 10.2 μm³represents an average between 9.7 μm, 8.0 μm, and 9.6 μm ⁴represents anaverage between 6.0 μm and 6.4 μm ⁵represents an average between 10.0μand 10.4 μm ⁶the second value is with no water in the glass bottle tosimulate a dry environment ⁷biaxially oriented polystyrene film⁸cationic epoxy lacquer is GQ26290F from B.A.S.F ⁹cast film ¹⁰same filmstructure as used in Ex 29 in Table 7 ¹¹represents an average between6.0 μm and 8.6 μm ¹²same film structure as used in Ex 36 in Table 7 ¹³80melt flow rate grade from The Dow Chemical Co. ¹⁴represents an averagebetween 7.9 μm and 10.0 μm ¹⁵same film structure as used in Ex 39 inTable 7 ¹⁶represents an average between 5.6 μm and 5.8 μm ¹⁷biaxiallyoriented monolayer polyethylene terephthalate (PET) same film structureas used in Comparative Ex N in Table 8 ¹⁸same film structure as used inEx 35 in Table 8 ¹⁹same film structure as used in Ex 30 in Table 8²⁰represents an average between 4.3 μm and 4.6 μm

The data in Table 6 demonstrate that the films currently used in ostomybag applications (Comp Ex A-F) have 3-methyl indole breakthrough times≧7 hrs. The EVOH coextruded film of Comp Ex G, which has been suggestedfor ostomy application, has a 3-methyl indole breakthrough time of 1hour, making it undesirable for ostomy applications, despite an oxygenpermeability comparable to the films of Comp Ex A-F.

The films of Comp Ex H, I, J, K, and L exhibit low oxygen permeability,but 3-methyl indole breakthrough times ≦3 hrs. The films of Ex 2, 4, 5,6, 15, and 16 exhibit high oxygen permeability, but have 3-methyl indolebreakthrough times ≧85 hrs. Therefore, the data of Table 6 clearlydemonstrate that no relationship exists between the oxygen permeabilityof a polymeric film and breakthrough times for 3-methyl indole. Thepolymers which are essentially glassy at the testing temperature (i.e.,PET-G, PET-G/SB and PET-G/SBS blends, PMMA, impact modified PMMA,PS/HIPS blends, SAN, PC, impact modified PC, PC/ABS alloy, ABS, and SAN)surprisingly provide the best barrier properties to 3-methyl indole.

TEST 3 Organic Sulfide (DEDS) Barrier Properties

The method for determining DEDS breakthrough time uses a permeation celland a mass spectrometry detector. Use a system consisting of apermeation cell, a flow-through hollow fiber membrane and a massselective detector (MSD) to measure DEDS odor permeation rates acrosspolymer films.

Instrumentation

The permeation cell is two stainless steel disks each having a machinedcavity on one face. Also on the face of the disk is an o-ring seatingsurface. The O-rings are KALREZ® perfluoroelastomer parts (DuPont DowElastomers L.L.C.). A polymer film, when clamped between the two disks,defines the upstream and downstream cavities. The upstream cavitycontains the permeant. Helium is swept through the downstream cavity andto the detector. The flow rate of the helium is approximately 4 mL/min.The exposed film surface area is 7.3 cm² and the volume of each cavityis approximately 4 mL. The two sides of the cell are clamped togetherusing plates with seats to center the two halves of the cell. Four boltsare tightened to ensure a seal between the O-rings and the test film.

Use a flow-through hollow fiber silicone membrane to concentrate thepermeant due to selectivity of the membrane. Place the permeation celland the hollow-fiber membrane in a HP5890 Series II Gas Chromatograph(GC) which is held at 40° C. for the permeation test. Plumb the hollowfiber to the transfer line for the mass selective detector (MSD). Theconditions for the MSD are listed below:

Instrument: Hewlett Packard 5971A MSD

Low mass: 50 High mass: 200 EMV offset: 0 Voltage: 2235 Threshold: 250Mode: Scan Tune file: ATUNE

Experimental Procedure

Load the film to be tested onto the bottom half of the cell. Protect thetest film from the permeant solution by covering the test film with apiece of LDPE film (approx. 25 μm thick). Place the top half of the cellon the LDPE film and bolt the cell together. Place the cell in the GCwith helium flowing through the bottom half of the cell to the hollowfiber membrane.

The permeant solution used for these experiments is 1 mL DEDS/10 mLethanol (EtOH) (approximately 9 wt % DEDS). Place a three mL aliquot ofthe solution in the top half of the cell. Data collection begins oncethe solution is in contact with the film. Continue experiments untilsteady-state permeation is achieved or for 24 hrs. The breakthrough timeis defined as the time at which the detector signal for ion mass 122reaches an abundance of 6000 counts.

The effect of the LDPE film on the permeation kinetics of the test filmis negligible. Breakthrough time of the polyethylene film, determined tobe five min, is an insignificant length of time compared to thebreakthrough times of the test films. The LDPE film protects the testfilm from the EtOH. If the skin layers of the film are polar in nature,such as EVA, the EtOH can plasticize the skin layers and effect theintegrity of the film as a whole.

The ion at m/z=122 is characteristic of DEDS. Choose this ion because ithas one of the highest relative abundances of the fragment ions in themass spectrum for DEDS. Also it is of high enough molecular weight so asto have minimal interference from other species present in the system.

The abundance is a relative number as the units are arbitrary and dependon the system. Calibrate the system using the calibration gas present inthe mass spectrometer as the tune gas. Tune the system prior to runningthe samples and retune it as necessary.

Table 7 shows the DEDS breakthrough time and the steady state relativepermeation rate of a series of polymeric films. These films containdifferent polymer resins as the barrier layer. The films of Comp Ex A,B, C, E, F, O are currently used in ostomy applications. The resins usedfor the fabrication of these films are listed in Table 5.

TABLE 7 DEDS DEDS relative Comp Ex/Ex Barrier Layer B.T. permeation rate(relative No. Film Structure Barrier Layer thickness (micron) (min.)unit) A LDPE/EVA/PVDC/EVA/LDPE PVDC 5.5¹  71 450 BLDPE/EVA/PVDC/EVA/LDPE PVDC 10.1² 136 200 C CPE/EVA/PVDC/EVA PVDC 9.1³139 >350  O LDPE/EVA/PVDC/EVA/LDPE PVDC 4.8  47 500 EEVA/MAH-g-EVA-2/GRIVORY□ amorphous co- 6.2⁴ 226 120 G21/MAH-g-EVA-2/EVAPA F EVA/MAH-g-EVA-2/co-PA-1/MAH-g- amorphous co- 10.2⁵ 190 250EVA-2/EVA PA M LDPE Reference 25  5 6000000   Sample (rating 5) 17LDPE-1/EVA/70:30 blend of GPPS-1 and 70:30 blend of 4.6 129 1000 ESI/EVA/LDPE-1 GPPS and ESI 18 LDPE-1-/EVA/70:30 blend of GPPS-3 and70:30 blend of 8.4 193 >600  ESI/EVA/LDPE-1 GPPS and ESI PLDPE-2/EVA/70:30 blend of 70:30 5.6  8 >4500  GPPS-3 and SIS- blend of1/EVA/LDPE-2 GPPS and SIS 19 LDPE-2/EVA/70:30 blend of 70:30 12.2  301400  GPPS-3 and SB/EVA/LDPE-2 blend of GPPS and SB 20 LDPE-2/EVA/70:30blend of 70:30 8.1 116 ˜350  SAN-1 and ESI/EVA/LDPE-2 blend of SAN andESI 21 LDPE-2/MAH-g-EVA-2/SAN- SAN 10.2⁷ 142 700 2/MAH-g-EVA-2/LDPE-2⁶22 LDPE-2/MAH-g-EVA-2/SAN- SAN 11.2 125 450 2/MAH-g-EVA-2/LDPE-2 23LDPE-2/MAH-g-EVA- PMMA 11.4  82 350 2/PMMA/MAH-g-EVA-2/LDPE- 2⁸ 24LDPE-2/MAH-g-EVA-2/PMMA- PMMA-IM 8.9  77 500 IM/MAH-g-EVA-2/LDPE-2 25LDPE-1/EVA/ABS/EVA/LDPE-1 ABS 7.1 112 500 26 LDPE-1/EVA/ABS/EVA/LDPE-1ABS 16.5 169 450 27 LDPE-2/MAH-g-EVA-2/PET- PET-G 8.1 166  65G/MAH-g-EVA-2/LDPE-2 28 LDPE-2/MAH-g-EVA-2/PET- PET-G 10.4 187  80G/MAH-g-EVA-2/LDPE-2 29 LDPE/EVA/75:25 blend of 75:25 7.3¹⁰  70 250PET-G and SBS/EVA/LDPE⁹ blend of PET-G and SBS 30 LDPE-2/EVA/85:15 blendof 85:15 4.5¹²  92  85 PET-G and SB/EVA/LDPE-2¹¹ blend of PET-G and SB31 LDPE-2/EVA/85:15 blend of 85:15 9.4 119 — PET-G and SB/EVA/LDPE-2blend of PET-G and SB 32 LDPE-2/EVA/70:30 blend 70:30 blend 8.1 115 >90of PET-G and of PET-G SB/EVA/LDPE-2 and SB 33 LDPE-2/EEA/PC- PC 4.8800 >45 4/EEA/LDPE-2 34 LDPE-2/EMA/PC- PC 5.8 1105  >18 1/EMA/LDPE-2 35LDPE-2/EMA/PC- PC 7.4 1315  — 1/EMA/LDPE-2¹³ 36 LDPE-2/EEA/PC/EEA/ PC¹⁵9.0¹⁶ >1440  — LDPE-2¹⁴ 37 LDPE-2/MAH-g-EVA-1/PC- impact 4.6 615 >400 IM-1/MAH-g-EVA-1/LDPE-2 modified PC 38 LDPE-2/EEA/PC-IM- impact 7.9916 >55 2/EEA/LDPE-2 modified PC 39 LDPE-2/MAH-g-EVA-2/PC- impact 5.7¹⁸⁷455 150 IM-2/MAH-g-EVA-2/LDPE- modified PC 2¹⁷ 40 LDPE-2/EEA/PC- PC-ABS15 1180  >30 ABS/EEA/LDPE-2 alloy 41 LDPE-2/MAH-g-EVA-2/PET- PET-G 9.2188  72 G/MAH-g-EVA-2/LDPE-2 42 LDPE-2/MAH-g-EVA-2/PET- PET-G 5.2 273 40 G/MAH-g-EVA-2/LDPE-2 43 LDPE-2/MAH-g-EVA-2/PET- PET-G 7.4 312  33G/MAH-g-EVA-2/LDPE-2 ¹represents an average of 4.0 μm and 7.1 μm²represents an average of 10.0 μm and 10.2 μm ³represents an average of9.7 μm, 8.0 μm, and 9.6 μm ⁴represents an average of 6.0 μm and 6.4 μm⁵represents an average of 10.0 μm and 10.4 μm ⁶same film structure asused in Ex 51 in Table 8 ⁷represents an average of 9.4 μm and 11.0 μm⁸same film structure as used in Ex 52 in Table 8 ⁹same film structure asused in Ex 7 in Table 6 ¹⁰represents an average of 6.0 μm and 8.6 μm¹¹same film structure as used in Ex 16 in Table 6 ¹²represents anaverage of 4.3 μm and 4.6 μm ¹³same film structure as used in Ex 15 inTable 6 ¹⁴same film structure as used in Ex 10 in Table 6 ¹⁵80 melt flowrate grade from The Dow Chemical Co. ¹⁶represents an average of 7.9 μmand 10.0 μm ¹⁷same film structure as used in Ex 11 in Table 6¹⁸represents an average of 5.6 μm and 5.8 μm

Table 7 demonstrates that films currently used for ostomy applications(Comp Ex A, B, C, E, F, O) have a DEDS breakthrough time ofapproximately 47 minutes or higher, and a DEDS relative permeation rateof 500 or lower. With the exception of the film of Comp Ex P, which hasa DEDS breakthrough time of 8 min and a DEDS P.R. of >4500, the films ofthe present invention (i.e., Ex 17-43) have DEDS breakthrough times andP.R.s in the same range or better than the values for the filmscurrently used for ostomy applications for comparable values of barrierresin thickness. The film of Ex 19 (GPPS-SB blend) has a DEDSbreakthrough time slightly lower than 47 min and the films of Ex 17 and18 (PS-ESI blend) have a DEDS P.R. higher than 500. However, a slightincrease in barrier layer thickness should be sufficient to bring thesevalues to the level of the films of Comp Ex A, B, C, E, F, O.

Table 7 further demonstrates that many amorphous polymers or blends areable to provide similar or better protection against the permeation ofDEDS and 3-methyl indole relative to traditional barrier polymers suchas those in Comp Ex A, B, C, E, F, O. The film of Comp Ex M, which is apure LDPE film, demonstrates that LDPE has very little barrierproperties to DEDS and therefore does not contribute to the barrierproperties of the other examples.

TEST 4 Hydrogen Sulfide H₂S Gas Barrier Properties

Measure the permeability of the films to H₂S gas at 40° C., using apermeation cell coupled to a PDHID (Photodiode Helium IonizationDetector) as described below:

Place a piece of film in a permeation cell. Control the temperature ofthe test cell at 40° C. Flow pure helium gas on one side of the film,while flowing a mixture of 1 wt % H₂S in helium on the other side of thefilm. Pass the flow of the pure helium gas through a PDHID detectorconnected to a data acquisition system that records the H₂Sconcentration in the gas stream as a function of time. Determine the H₂Sbreakthrough time and the steady state permeation rates on thetime/concentration curve. Calibrate the system with a H₂S gas mixture ofknown concentration.

Table 8 shows the H₂S breakthrough time and the steady state permeationrate of a series of polymeric films. These films contain differentpolymer resins as the barrier layer. The film of Comp Ex C is currentlyused in ostomy applications. The resins used for the fabrication ofthese films are listed in Table 5.

TABLE 8 Barrier H₂S Com Layer Permeation Ex/ Thick- H₂S Rate Ex. Barrierness B.T. (cm³/day · No. Film Structure Layer (μm) (sec) m²) CCPE/EVA/PVDC/EVA PVDC 9.1 450 3.55 44 LDPE-2/MAH-g- PC 6.0  68 192EVA-2/PC/MAH-g- EVA-2/LDPE-2 45 LDPE-2/MAH-g- PET-G 8.0 263 24.3EVA-2/PET-G/MAH- g-EVA-2/LDPE-2 41 LDPE-2/MAH-g- PET-G 9.2 155 34.0EVA-2/PT-G²/MAH- g-EVA-2/LDPE-2 46 LDPE-2/MAH-g- impact 6.0  65 168EVA-2/PC-IM- modi- 2³/MAH-g-EVA- fied PC 2/LDPE-2 47 LDPE-2/MAH-g-impact 4.6  73 162 EVA-2/PC-IM- modi- 1/MAH-g-EVA- fied PC 2/LDPE-2 48LDPE-2/MAH-g- ABS 6.0  65 116 EVA-2/ABS/MAH-g- EVA-2/LDPE-2 49LDPE-1/EVA/HIPS- HIPS 10  53 162 1/EVA/LDPE-1 21 LDPE-2/MAH-g- SAN 10.2195 70 EVA-2/ SAN-2/MAH-g-EVA- 2/LDPE-2 23 LDPE-2/MAH-g- PMMA 11.4 2758.2 EVA-2/PMMA/MAH- g-EVA-2/LDPE-2 N PET PET 13 185 10.9 ¹represents anaverage of 9.7 μm, 8.0 μm, and 9.6 μm ²5 PET-G layers separated by alayer of adhesion resin. The total thickness of these 5 PET-G layers isreported in Table ³represents an average of 9.4 μm and 11.0 μm

Table 8 shows that the films used in Ex 41 and 45, with a PET-G barrierlayer, and the film used in Ex 23, with a PMMA barrier layer, have H₂Sbreakthrough times and P.R.s in the same magnitude as a film currentlyused for ostomy application (Comp Ex C). The film of Ex 21 has an H₂Sbreakthrough time of about half of that of the film used in Comp Ex Cand 20 times its P.R. The film of Comp Ex N (PET) has a P.R. 3 timeshigher and an H₂S breakthrough time approximately half of that of thefilm of Comp Ex C.

PET is a semi-crystalline polyester with a melting point ofapproximately 255° C. and therefore must typically be processed at anextrusion temperature of 270° C. to 290° C. PET-G (Ex 41 and 45) is anessentially amorphous polyester with a Tg of approximately 81° C. andcan therefore be processed at lower extrusion temperatures of 190° C. to220° C. This extrusion temperature range is closer to the temperaturestypically used for extruding polyolefins and elastomers. Therefore, itis much easier to coextrude PET-G with these resin families compared toPET (“Film Extrusion Manual”, Chapter 19G: Polyester, page 533, TAPPIPress 1992). PET-G also has a lower modulus of elasticity and a higherimpact resistance than PET (Eastman Chemical product literature, ref.PPM-204 (May 1996) lists following values: Flexural Modulus=2,100megapascals (MPa) versus 2,500 MPa; Izod impact strength =102 J/m versus51 J/m for PET-G copolyester versus PET homopolymer). Therefore, filmswith a low rigidity (i.e., high flexibility) are more easily achievedwith PET-G than with PET. The films used in Ex 44 and 47-50 have H₂Sbreakthrough times 7 times shorter and P.R.s 33 to 47 times higher thanthe film of Comp Ex C.

Based upon this data, it is believed that PET-G and PMMA have a goodcombination of odor barrier properties for small molecules (e.g., H₂S0.40 nm molecular diameter), larger molecules (e.g., DEDS 0.58 nmmolecular diameter) and large molecules (e.g. 3-methyl indole 0.78 nmmolecular diameter). Therefore, they are well-suited for ostomy bagapplications. The other amorphous polymers (i.e., PC, impact modifiedPC, ABS, SAN, PS, and blends) have good barrier properties to moleculeswith a molecular diameter of approximately 0.58 nm and higher (DEDS and1- or 3-methyl indole), but are not as well-suited for ostomyapplications due to their low barrier properties to small molecules(e.g., H₂S). Therefore, these polymers are useful for applications wherebarriers to only larger molecules (e.g., DEDS and 3-methyl indole) arerequired. For example, in the packaging of odorous chemicals, inprotective clothing applications and in trans-dermal drug deliverysystems (TDDS).

TEST 5 1% Secant Modulus and Oxygen Permeability of PET-G Blends

As described previously, the PET-G resin can be blended with softerpolymers in order to increase its softness and resistance toflex-cracking. For example, compound the PET-G resin listed in Table 5with 25 wt % of a softer polymer resin in a ZSK-30 compounder. Let thecompounded pellets down at 32 wt % and 64 weight percent with pure PET-Gresin and feed it into a 30 mm diameter 24 L/D extruder. Extrudemonolayer cast films of 30 μm and 60 μm thicknesses through a 250 mmwide die. Measure the 1% secant modulus and oxygen permeability of thesefilms and report the data in Table 9.

TABLE 9 Oxygen Permeability % Flexible (cm³/ 1% modulus (MPa) FlexibleResin in m²-day-atm for 10 (average of MD & Resin PET-G Film μm ofresin) TD) SIS-2 0 698 1682 SIS-2 8 896 1442 SIS-2 16 1229 1316MAH-g-EMA 0 698 1682 MAH-g-EMA 8 989 1328 MAH-g-EMA 16 1115 1061 EMAGMA0 698 1682 EMAGMA 8 900 1411 EMAGMA 16 1162 1092 MAH-g-SEBS 0 698 1682MAH-g-SEBS 8 1040 1405 MAH-g-SEBS 16 970 1390

The data in Table 9 show that it is possible to reduce the modulus of aPET-G resin by blending with a more flexible resin. This allows theproduction of a less rigid film if high modulus is problematic. On theother hand, the blend has an oxygen permeability greater than that ofthe PET-G resin. Although the oxygen permeability is not an accuratepredictor for the permeability of the film to other gases and chemicalcompounds, it is believed that, for the same polymer type, the relativevariations of oxygen permeability can be useful in predicting therelative variations of permeability and B.T. to other gases and chemicalcompounds. For example, films of Ex 27 and 32 of Table 7 contain abarrier layer of 8.1 μm pure PET-G (Ex 27) and of 8.1 μm of a 70/30 wt %blend of PET-G/SB (Ex 32). Report the permeabilities to oxygen and DEDSof these two films in Table 10.

TABLE 10 DEDS relative Oxygen Permeability DEDS B.T. permeation rate ExNo. (cm³/m²-day-atm) at 23° C. (min) (cm³/day-m²) 27 467 166 65 32 675115 >90

The oxygen permeability of the film of Ex 32 containing the PET-G blendis 45% higher than the pure PET-G resin film of Ex 27. The DEDS B.T. andP.R. are also altered by approximately 45% and 40%, respectively, byblending of the SB resin in the PET-G resin.

II. Acoustical Properties

As stated previously, in addition to barrier properties, it is oftendesirable that a polymeric film not emit noise when crumpled. Forexample, in ostomy or incontinence applications, it is desirable thatthe ostomy or incontinence bag not emit noise. However, when crumpled,most polymeric films emit noise. In the case of multilayer barrierfilms, when polymers of high and low rigidities or modulus are combined,the multilayer film is significantly more noisy when crumpled than arefilms of the same thickness made only with the lowest modulus polymer.

TEST 6 Comparison of Noise and Modulus of Multilayered Films

A demonstration of the phenomenon that when polymers of high and lowrigidities or modulus are combined in a multilayer film, the multilayerfilm is significantly more noisy when crumpled than are films of thesame thickness made only with the lowest modulus polymer is shown in thefollowing Comp Ex Q to W in Tables 12 and 13, wherein the composition ofthe films is described in Table 11.

Coextrude five layer symmetrical cast films of layer configurationA/B/C/B/A with LDPE or EVA skins and a rigid core layer of PET-G, ABS,amorphous PA or PC. These films have two tie layers, each representing7.5% of the total film thickness. Also prepare monolayer cast films ofthe same composition as the skin layers and of comparable thickness.Table 11 lists the composition of these films. All resins are describedin Table 5.

TABLE 11 Core Total Skin Layer Thick- Comp. Layers Tie Core Thicknessness Ex. A Layers B Layer C μm μm Film Type Q LDPE-2 — — — 75 monolayerR LDPE-2 MAH-g- PET-G 7.5 78 5 layers EVA-2 S LDPE-2 MAH-g- ABS 7.5 78 5layers EVA-2 T LDPE-2 MAH-g- co-PA-1  6¹   76 5 layers EVA-2 U LDPE-2EMA PC-3 8   95 5 layers V EVA-4 — — — 72 monolayer W EVA-4 MAH-g- PET-G6.5 90 5 layers EVA-2 ¹in this film, the barrier layer is split into 5alternating layers “barrier/tie”. The sum of these barrier layers isreported

There is a high difference in modulus (rigidity) between the skin andthe core resins of these films as shown in Table 12.

Determination of the Storage Modulus (G′) and Tangent Delta by DynamicMechanical Spectroscopy (D.M.S.)

Determine the G′ of the films in Table 12 as follows:

Make dynamic mechanical measurements (i.e., G′ and Tan Δ values) usingone of two Rheometrics RDS-II instruments (S/N 024-12 and 024-40)running under Rheos 4.4.4 software for machine control and datacollection. Test all samples using a dynamic temperature ramp profile,from −100° C. to approximately 150° C. at 2° C./min with a torsionalfrequency of 10 radians per second (rad/sec) and strain of 0.02%.Compression mold individual specimens prior to for testing. Specimendimensions are approximately 12.7×3.2×57.2 mm (0.5×0.125×2.25 in).

TABLE 12 Storage modulus G′ at 20° C. G′ (10E-5 RESIN Newton/cm²) LDPE-21.57E + 09 EVA-4 1.20E + 08 PET-G  7.3E + 09 ABS 1.03E + 10 co-PA-11.08E + 10 PC-3 8.64E + 09

Measure the noise of these films and report the results in Table 13.

Determine the noise of the films of Table 13 as follows:

Cut a 10×10 cm size sample in the film, with the machine (MD) andtransverse direction (TD) parallel to the sides of the sample. Fix thespecimen with double side adhesive tapes on two circular holders of adiameter of 32 mm and 90 mm distant of from each other. The film has theshape of a vertical cylinder (32 mm diameter) with one slit along itsaxis. The film MD is parallel to the axis of the cylinder. Make surethat folds from the cylindrical film sample are eliminated. The bottomcircular holder is stationary while the upper holder is connected to analternating drive mechanism.

Place a microphone 17 mm from the edge at half height of the filmcylinder, at 90° from the slit. Connect the microphone to a CEL 393noise analyzer having an octave frequency filter. Set the noise analyzerin “P” (peak) mode, range 2. Enclose the whole set-up, with theexception of the motor of the drive unit and the noise meter, in a soundinsulated box (15 mm plywood/3 mm lead/8 cm rockwool from outside toinside). Internal dimensions of the box are 33 cm×33 cm×40 cm(length×width×height). After starting the motor, the film makes analternative flexing motion with an angle of 65 degrees at the flexingfrequency of 0.6 Hz. Record the noise made by the flexing motion of thefilm in the octave frequency bands from 16 Hz to 16 kHz in the decibel Ascale [dBA]. Make 2 to 4 measurements and calculate an average for eachfrequency band. Conduct the test at ambient temperature (approximately20° C.).

TABLE 13 Noise in dBA for different octave frequency bands Comp. 63 125250 500 1 2 4 8 16 EX Hz Hz Hz Hz kHz kHz kHz kHz kHz Q 36.2 46.2 58.560.8 62.5 65.1 68.4 61.9 48.9 R 49.3 54.4 66.6 77.3 76.1 78.1 75.7 71.065.4 S 47.7 54.5 65.6 72.3 75.2 78.6 76.6 71.5 63.3 T 45.2 54.1 65.070.9 72.1 77.4 75.1 71.8 64.2 U 50.9 58.0 69.6 73.8 75.6 77.3 75.3 71.463.6 V 37.6 38.1 41.6 44.3 43.0 47.0 42.8 35.5 25.7 W 38.8 50.3 57.562.9 69.2 74.1 73 68.2 54.6

Comp Ex R, S, T, U and W are significantly noisier than the films ofComp Ex Q and V which do not include the thin core layer of rigid resin.The higher noise of the films containing the rigid core layer is due toa lower “sound reduction index” or “SRI” of the film resulting from theincorporation of a layer of higher stiffness in the structure. Reducingthe stiffness of a structure is a known method to increase its SRI.(See, for example, Woods Practical Guide to Noise Control, Fifthedition, March 1972, page 117. Published by Woods Acoustics, a divisionof Woods of Colchester Limited, UK). It may therefore be advantageous tofind a method to reduce the noise of these coextruded structurescontaining a rigid layer. Rigid layer means that the G′ modulus of thislayer is ≧2×10⁴ N/cm².

TEST 7 A) Determination of Noise for Multilayer Polymeric Films

Prepare six symmetrical 5-layer, co-extruded cast films A/B/C/B/A withthe same rigid barrier layer (layer C), but with skin layers ofdifferent rigidities. These films have one ?PET-G co-polyester barrierlayer and 2 tie layers representing 15 percent of the total thickness.Table 14 describes these films, and Table 22 reports the G′ and Tan Δvalues of the skin polymers.

TABLE 14 Films Description Barrier Comp. Total Layer Ex. or Tie BarrierThickness Thickness Ex No. Skin Layers A Layers B Layer C (μm) (μm) XLDPE-2/ADD-1 MAH-g- PET-G 75 5.0 (96/4%) EVA-2 Y ITP-4/ADD-1 MAH-g-PET-G 72 6.0 (96/4%) EVA-2 Z EMA/ADD-1 MAH-g- PET-G 75 6.3 (96/4%) EVA-2AA EMA/ITP- MAH-g- PET-G 75 5.o 4/ADD-4 EVA-2 ® (48/48/4%) 3860 50PP/ADD-1 MAH-g- PET-G 70 8.3 (96/4%) EVA-2 51 PP/ITP-4/ADD- MAH-g- PET-G78 6.9 1 (48/48/4%) EVA-2 **Typical compositions of skin layers of Comp.Ex. Y is described in the patent Application WO 95/07816 entitled“Multilayer Barrier Film”

The noise of these films was measured and is reported in Table 15,wherein the noise is determined as described previously in Test 6.

TABLE 15 Film noise level in dBA versus Octave Frequency band Comp.Ex./- 63 125 250 500 1 2 4 8 16 Ex No. Hz Hz Hz Hz kHz kHz kHz kHz kHz X36.8 48.3 63.7 72.9 71 77.7 75.5 69.7 59.8 Y 38.5 48.4 56 59.6 62.4 7274 67.6 57.9 Z 37.3 43.9 52.2 57 58.2 65.3 69.9 63.2 50.2 AA 37.9 45.554.8 60.5 60.6 69.8 75 67.2 49.2 50 38.1 42.6 51.3 56 57.4 65.4 67 56.640.7 51 38.5 45.6 54.6 57.5 60.9 66.6 68 61.1 39.3

Table 15 shows that, surprisingly, the quietest films are not the onesmade with the skin resin composition of the lowest G′ modulus. Ex 50 and51 are the quietest films in almost the whole frequency spectrumalthough their skin resins have a G′ modulus significantly higher thanthose of Comp Ex Y, Z and AA. The Tan Δ value of the skin resins of afilm in the −5° C. to +15° C. temperature range plays a dominant role inreducing the noise of the coextruded structure. Ex 50 and 51 have thehighest Tan Δ in this temperature range and are, therefore, quietestfilms. This clearly demonstrates why Ex 50 and 53 are significantlyquieter than the films of Comp Ex X, Y, Z and AA.

Blending resins does not significantly alter the final result, as seenwith the film of Ex 51 which has a noise intermediate between the filmsof Comp Ex Y and Ex 50 which are made with each of its skin components.

The quietest films are those that contain a polymeric resin having a TanΔ value ≧0.25 at a temperature within the range between −5° C. and 15°C. or ≧0.32 at a temperature within the range between −12° C. and −5° C.

Surprisingly, when the co-extruded films contain some resins with goodnoise reduction characteristics (e.g., high Tan Δ value in the −12° C.to +15° C. temperature range) and relatively low G′, thicker films are,contrary to expectations, quieter than thinner films at highfrequencies. Test 7-C below supports this observation with Comp Ex ACand AD, as well as Ex 52 and 53.

At least one skin layer preferably comprises from 75 to 25 wt % of lowcrystallinity PP copolymer and from 25 to 75 wt % of a blend of lowcrystallinity homogeneous EAO copolymer and LLDPE or ULDPE. Also, thetie layers preferably each represent 3 to 15% of the total filmthickness and are formed from an EVA or EMA copolymer having aco-monomer content ≧20 wt %.

B) Noise Determination for Multilayer Polymeric Films

These films are 5-layer, co-extruded cast films A/B/C/B/A with PET-Gco-polyester barrier layer (layer C). The films of Comp Ex AB and AChave the same skin compositions, but different skin thickness; the filmsof Ex 52 and 53 have another skin composition and different skinthickness. All films have one barrier layer and two tie layersrepresenting 15% of the total thickness. Table 16 describes the films.Table 22 reports the G′ and Tan Δ values of the skin polymers.

TABLE 16 Films Description Barrier Total Layer Comp. Thick- Thick- Ex/ExSkin Tie Barrier ness ness No. Layers A Layers B layer C (μm) (μm) ABEVA-1/EVA-2/ADD-1 MAH-g- PET-G 80 5.0 (72%/24%/4%) EVA-2 ACEVA-1/EVA-2/ADD-1 MAH-g- PET-G 95 4.8 (72%/24%/4%) EVA-2 52 PCP-2/ADD-1MAH-g- PET-G 79 9.4 (92%/8%) EVA-2 53 PCP-2/ADD-1 MAH-g- PET-G 90 10.0(92%/8%) EVA-2

The noise of these films is reported in Table 17, wherein the noise isdetermined as described previously in Test 6.

TABLE 17 Film noise level in dBA versus Octave Frequency band Comp.Ex/Ex 63 125 250 500 1 2 4 8 16 No Hz Hz Hz Hz kHz kHz kHz kHz kHz AB37.2 46 53.3 58.9 61.7 70.6 73.5 64 55.1 AC 37.5 48.8 59.7 63.6 65.174.2 75.6 69.1 58.1 52 37.6 41.1 49.7 55.6 58.6 67.6 66.9 56.6 37.2 5337.9 44.5 53.8 57.1 60.1 66 64.9 55.1 31

The film of Comp Ex AC is noisier than the film of Comp Ex AB at allfrequency ranges, while the film of Ex 53 is noisier than the film of Ex52 only up to 1 kHz, but is quieter from 2 to 16 kHz (i.e., the mostannoying frequencies for the human ear).

C) Determination of Noise for Multilayer Polymeric Films

Prepare eight symmetrical 5-layer, co-extruded cast films A/B/C/B/A withthe same rigid barrier layer, but with skin layers of different G′ andTan Δ values. These films have one PET-G co-polyester barrier layer andtwo tie layers representing 15% of the total thickness. Table 18describes these films. Table 22 provides the G′ and Tan Δ values of theskin polymers can be found in Table 22, and in FIGS. 1, 2, 4, 7, 8, 9and 10. Table 18 also reports Comp Ex X with LDPE skin layers as acontrol film.

TABLE 18 Film Descriptions Barrier Comp. Total Layer Ex/Ex Skin TieBarrier Thickness Thickness No Layers A Layers B Layer C (μm) (μm) XLDPE-2 MAH-g- PET-G 75 5.0 EVA-2 AD PP-EPDM/ MAH-g- PET-G 75 6.0 ADD-1EVA-2 (98/2%) 54 PP/PP- MAH-g- PET-G 80 7.5 EPDM/ADD-1 EVA-2 (72/24/4%)55 PCP-3/ADD-1 MAH-g- PET-G 85 6.0 (92/8%) EVA-2 56 PCP-2/ADD-1 MAH-g-PET-G 79 9.4 (92/8%) EVA-2 57 PP/PCP- MAH-g- PET-G 77 10 1/ADD-1 EVA-2(72/24/4%) 58 PP/PCP-2/ EMA PET-G 74 8.5 ADD-1 (72/24/4%) 59 PCP-1/ITP-EVA-3 PET-G 76 9.2 4/ADD-1 (46/46/8%)

Table 19 summarizes noise measurements of these films, with noise beingdetermined as in Test 6.

TABLE 19 Film noise level in dBA versus Octave Frequency band Comp.Ex/Ex 63 125 250 500 1 2 4 8 16 No. Hz Hz Hz Hz kHz kHz kHz kHz kHz X36.8 48.3 63.7 72.9 71 77.7 75.5 69.7 59.8 AD 43.7 50.7 55.9 57.9 57.864.7 66.7 64.1 52 54 36.9 43.5 52.4 55.3 59.2 66.9 65.3 58.3 38.8 5537.2 43.8 49.2 52.2 53.9 61.2 60.9 48.6 28.4 56 36.3 43.6 51.2 55.7 57.967.2 66.9 57.1 41.6 57 37.9 46 55.7 59.6 61 63.8 64.3 54 37.7 58 38 41.553.2 59.4 60.6 67 68.7 58.5 49.6 59 36.4 46.4 54.1 57.3 58.8 65 65.862.4 49.3

The data of Table 19 clearly shows that the film of Comp Ex AD isquieter than the film of Comp Ex X mainly because of the G′ value of itsskin resin which is approximately 30-40 times lower. On the other hand,the films of Ex 54 to 59 are essentially quieter than the films of CompEx X and AD, mainly in the frequency range of 1 kHz and above becausetheir composition contains a significant proportion of a polymer havinga Tan Δ value ≧0.25 at a temperature within the range between −5° C. and15° C. or ≧0.32 at a temperature within the range between −12° C. and−5° C., while their G′ value is in the same range as LDPE (See Table22). Low crystallinity PP homo- or copolymer resins, as used in Ex 54 to59, are particularly efficient noise dampening polymers. Lowcrystallinity PP, as used herein, means that the heat of fusion (Hf) ofthe resin is significantly lower than that of regular isotactic PP, e.g.≦50 J/g.

D) Noise Determination for Multilayer Polymeric Films

Prepare four symmetrical 5-layer, co-extruded cast films A/B/C/B/A withthe same rigid barrier layer, but with skin layers of different G′ andTan Δ values. These films have an amorphous co-polyamide barrier layerand two tie layers representing 15% of the total thickness. The G′ andTan Δ values of the skin polymers can be found in Table 22.

TABLE 20 Film Descriptions Barrier Comp. Total Layer Ex/Ex. Tie BarrierThickness Thickness No. Skin Layers A Layers B Layer C (μm) (μm) AELDPE-2 MAH-g- co-PA-1 86 9.6(**) EVA-2 AF EVA-1/ADD-1 MAH-g- co-PA-1 7510.0 (95%/5%) EVA-2 60 PCP-2/ITP- MAH-g- co-PA-1 75 7.5 4/ADD-1 EVA-2(46%/46%/8%) 61 PCP-2/ITP- MAH-g- co-PA-1 75 9.0 4/ADD-1 EVA-2(46%/46%/8%) **: in this film, the barrier layer is split into 5alternating layers “barrier/tie”. The sum of these barrier layers isreported

Table 21 summarizes noise measurements of these films, with noise beingdetermined as in Test 6.

TABLE 21 Film noise level in dBA versus Octave Frequency band Comp.Ex/Ex 63 125 250 500 1 2 4 8 16 No. Hz Hz Hz Hz kHz kHz kHz kHz kHz AE51.8 56.3 66.4 76.5 77.3 78.6 75.4 72.6 66.2 AF 42.5 54.1 66.7 70.7 74.676.6 76.7 75.2 65.8 60 36.0 39.5 50.5 52.7 55.8 64.4 61.8 56.1 42.3 6138.9 44.6 58.0 60.0 63.7 73.3 70.6 68.3 54.9

Ex 60 and 61 are significantly quieter than Comp Ex AE and AF. Thisclearly shows that the significant noise reduction of multilayer filmsobtained by the use of polymeric resin having a Tan Δ value ≧0.25 at atemperature within the range between −5° C. and 15° C. or ≧0.32 at atemperature within the range between −12° C. and 5° C. in the filmcomposition is not restricted to films containing a layer of PET-G, butis also achieved by combining resins of high and low modulus in a samefilm structure.

Measure the noise of all Ex at room temperature (approx. 20° C.). It isanticipated that if the noise is measured at a different temperature,the same noise reduction effect shall be obtained with polymers having aTan Δ value ≧0.25 in a temperature range shifted by the same temperaturedifference.

Table 22 gives the Maximum Tan Δ values, G′ values, and Tan Δ values atselected temperatures for resins used in Tests 6-8, with thedetermination of the G′ and Tan Δ values as in Test 6. Skilled artisansrecognize that G′ and Tan Δ values are readily portrayed as curvesrather than discrete values. The values shown in Table 22 merelyillustrate points on the curve and do not limit this invention to thosepoints. The invention includes all points on the curve that meet thecriteria specified herein.

TABLE 22 Maximum Tan Δ, G′ and Tan Δ Values at selected Temperatures MaxTan Δ Tan Δ value at selected temperatures Resin ° C. value −20° C. −10°C. 0° C. 10° C. 20° C. 30° C. 40° C. PP 2.2 0.46 0.03 0.068 0.43 0.3130.16 0.125 0.13 PCP-1 1.6 0.41 0.028 0.074 0.395 0.291 0.167 0.12 0.115PCP-2 1.5 0.59 0.033 0.099 0.575 0.366 0.186 0.134 0.137 PCP-3 0.2 0.640.037 0.14 0.644 0.349 0.178 0.135 0.137 EVA-4 −19 0.28 0.27 0.249 0.210.154 0.08 0.053 0.06 ITP-4 −15 to 0.19 0.19 0.19 0.19 0.168 0.12 0.0720.05 0¹ LDPE- 63 0.23 0.08 0.092 0.01 0.11 0.13 0.14 0.17 2 EMA −21.60.317 0.312 0.24 0.189 0.123 0.066 0.049 0.053 PP- −21 0.305 0.3 0.2180.165 0.122 0.077 0.066 0.078 EPDM EVA-1 −15 0.20 0.197 0.20 0.192 0.1880.158 0.10 0.06 EVA-2 −18.5 0.23 0.23 0.217 0.21 0.189 0.125 0.071 0.06Storage modulus G′ at selected temperatures (G′ in 10E⁻⁵ N/cm²) Resin−20° C. −10° C. 0° C. 10° C. 20° C. 30° C. 40° C. PP 1.10E+ 1.01E+4.20E+ 8.18E+ 4.70E+ 3.60E+ 2.40E+08 10 10 09 08 08 08 PCP-1 1.12E+9.91E+ 3.24E+ 8.91E+ 5.34E+ 3.97E+ 2.97E+08 10 09 09 08 08 08 PCP-21.05E+ 8.94E+ 1.89E+ 4.01E+ 2.41E+ 1.74E+ 1.27E+08 10 09 09 08 08 08PCP-3 1.08E+ 8.50E+ 1.41E+ 3.27E+ 2.05E+ 1.58E+ 1.23E+08 10 09 09 08 0808 EVA-4 1.20E+ 4.82E+ 2.50E+ 1.56E+ 1.20E+ 9.25E+ 5.70E+07 09 08 08 0808 07 ITP-4 1.45E+ 8.87E+ 5.71E+ 3.99E+ 2.92E+ 2.33E+ 1.72E+08 09 08 0808 08 08 LDPE- 4.68E+ 3.53E+ 2.70E+ 2.10E+ 1.57E+ 1.18E+ 8.11E+08 2 0909 09 09 09 09 EMA 8.60E+ 3.66E+ 2.17E+ 1.40E+ 1.08E+ 9.00E+ 6.45E+07 0808 08 08 08 07 PP- 2.91E+ 1.32E+ 8.22E+ 5.38E+ 4.11E+ 3.46E+ 2.55E+07EPDM 08 08 07 07 07 07 EVA-1 1.98E+ 1.90E+ 5.80E+ 3.57E+ 2.47E+ 1.85E+1.50E+08 09 09 08 08 08 08 EVA-2 1.70E+ 8.18E+ 4.54E+ 2.81E+ 1.97E+1.47E+ 9.68E+07 09 08 08 08 08 08 ¹broad peak

III. Heat Seal Strength Properties

As described previously, it may be desirable for the end use applicationto seal some of the multi-layer films, for example, to produce bags. Theseal strength of some skin polymer compositions may be too low when thefilm is sealed to itself or to other polymers. A higher seal strengthmay be obtained by adding a sealant layer to the outermost layer of thefilm, or by blending into the outermost layer a polymer that improvesthe seal strength.

TEST 9 Determination of Heat Seal Strength of Mulilayered PolymericFilms

Table 23 (5-layer, co-extruded films A/B/C/B/A with two tie layers, B,representing 15% of the total thickness) demonstrates that a higher sealstrength may be obtained by blending into the composition some otherpolymer that improves the seal strength. In this regard, blendscomprising a low crystallinity EAO copolymer and LLDPE or ULDPE areadvantageous and preferred.

Determine the heat seal strength of the films in Table 23 as follows:

Heat seal two pieces of film together on a laboratory heat sealer asdetailed below.

Use 20 N/cm² sealing pressure, and 1.5 sec sealing time. Heat the uppersealing jaw at 180° C. (film/film) or 225° C. (film/LDPE), while thelower jaw is at 50° C. Interpose a 13 μm thick polyester film betweenthe film and the sealing bars to prevent sticking. The seal is parallelto the film TD. Cut 25.4 mm wide heat sealed specimens and put them inthe clamps of a tensile tester having 50 mm distance between the, twoclamps. Pull the two sides of the seal apart at a speed of 508 mm/min inthe film's MD. Record the maximum force required to break the specimenas the seal strength. For the seal strength film/film, seal the film onitself. For the seal strength film/LDPE, seal the film on a LDPE basedfilm (70 μm thickness, a blend of 75 wt % of LDPE melt index (M.I.)=1.75g/10 min, density (d)=0.924 g/cm³ and 25 wt % of LLDPE (octenecopolymer) M.I.=2.3 g/10 min, d=0.917 g/cm³). Place the LDPE film on thelower jaw of the heat sealer to prepare the seal.

TABLE 23 Composition and Seal Strength of Films Total Barrier Layer SealStrength Seal Strength Ex Barrier Thickness Thickness Film/Film Film/No. Skin Layers A Tie Layers B Layer C (μm) (μm) (N/25 mm) LDPE (N/25mm) 50 PCP-1/ MAH-g-EVA-2 PET-G 70 8.3 14.5  1.1 ADD-1 (96/4%) 57PCP-1/PCP-2/ADD-1 MAH-g-EVA-2 PET-G 77 10 10.4  1.5 (72/24/4%) 51PCP-1/ITP-4/ MAH-g-EVA-2 PET-G 78 6.9 17.0 13.9 ADD-1 (48/48/4%) 62PCP-1/ITP-4/ADD-1 EVA-3 PET-G 80 7.0 22.3 18.7 (46/46/8%) 63PCP-2/ITP-4/ EVA-3 PET-G 75 6.0 18.0 17.2 ADD-1 (69/23/8%) 64 PCP-2/EVA-3 PET-G 80 6.0 21.4 not determined ITP-4/ITP-1/ADD-1/ADD-4/ADD-3/ADD-2 (46/21.3/21.2/6/3.5/2%) 65 PCP-2/ EVA-3 PET-G 75 6.020.2 not determined ITP-4/ULDPE-3/ADD-1/ ADD-4/ADD-3/ADD-2(46/21.3/21.2/6/3.5/2%) 66 PCP-2/ EVA-3 PET-G 81 7.0 19.6 not determinedITP-3/ULDPE-3/ADD-1/ ADD-4/ADD-3/ADD-2 (46/10.6/31.9/6/3.5/2%) 67 PCP-2/EVA-3 PET-G 75 7.0 21.1 not determined ITP-2/ULDPE-1/ADD-1/ADD-4/ADD-3/ADD-2 4420 (46/19.1/23.4/6/3.5/2%) 68PCP-2/ITP-3/ULDPE-2/ADD-1/ EVA-3 PET-G 74 8.0 20.4 not determinedADD-4/ADD-3/ADD-2 (46/17/25.5/6/3.5/2%)

Comparing Ex 51 and 62 to 68 with Ex 50 and 57 shows that blending somelow crystallinity homogeneous EAO copolymer or some ULDPE and lowcrystallinity homogeneous EAO copolymer in the low crystallinity PPimproves the seal strength of the films.

Ex 50 and 57 have acceptable heat seal strength on themselves, but verylow seal strength onto LDPE, while the films of Ex 51, 62 and 63 havestronger seal strength on themselves as well as on LDPE. Thesecompositions are also advantageous when the film must be sealed on apolyolefin article like LDPE.

III. Tie Resin Selection

Alternative resins to EVA copolymers can be used as tie resins between aPET-G-based layer and a polyolefin-based layer in a coextruded filmstructure. Table 24 (5-layer, co-extruded films, A/B/C/B/A with two tielayers, B, representing 15% of the total thickness) data demonstratethat adequate seal strength can be obtained by using EMA copolymersinstead of EVA.

TABLE 24 Composition and Seal Strength of Films Barrier Total Layer SealStrength Ex. Skin Tie Barrier Thickness Thickness Film/Film No. Layers ALayers B Layer C (μm) (μm) (N/25 mm, MD) 69 PCP-2/ITP-4/ EMA PET-G 757.5 23.7 ADD-1 (46/46/8%) *Trademark of The Dow Chemical Company

Other tie resins useful in the present invention can be selected fromMAH- or glycidyl methacrylate grafted EVA, EMA or EBA, ethylene-acrylicester-glycidyl methacrylate terpolymers, ethylene-glycidyl methacrylatecopolymers, ethylene-acrylic ester-maleic anhydride terpolymers, SBcopolymers, EVACO terpolymers, styreneisoprene copolymers and blendsthereof.

Ex 70-74

Prepare four five-layer symmetrical coextruded films (Ex 70-73) and oneseven-layer symmetrical coextruded film (Ex 74). The five layer filmshave an A/B/C/B/A structure and the seven layer film has anA/B/C/D/C/B/A structure. Table 25 provides layer thickness andcomposition for Ex 70-73. The barrier core layer for Ex 70 constitutesPET-G. The barrier core layer for Ex 71-74 constitutes a blend of PET-Gand APE-1. For Ex 74, the respective layer compositions and thicknessesare: A=93 wt % ITP-1 and 7 wt % ADD-1, 8 μm per layer; B=100 wt % PCP-2,26.5 μm per layer; C=100 wt % EVA-3, 5.6 μm per layer; and D=70 wt %PET-G and 30 wt % APE-1 , 4.8 μm.

TABLE 25 Ex No. Skin Layer A Tie Layer B Barrier Layer C 70PCP-2/ITP-2/ULDPE-1/ADD-1 EVA-3, 7.5 μm PET-G, 10.4 μm(46/19.2/23.3/11.5%) 41.3 μm 71 PCP-2/ITP-2/ULDPE-1/ADD-1 EVA-3, 7.5 μmPET-G/APE-1 (70/30) 9.9 μm (46/19.2/23.3/11.5%) 39.6 μm 72PCP-2/ITP-2/ULDPE-I/ADD-1 MAH-g-EVA-2/ADD-1 PET-G/APE-1 (50/50) 4.5 μm(46/21.2/25.8/7%) 38.9 μm (98/2%), 7.5 μm 73 PCP-2/ITP-2/ULDPE-1/ADD-1EVA-3, 7.5 μm PET-G/APE-1 (50/50) 6.7 μm (46/21.2/25.8/7%) 40.8 μm

Subject the multilayer films of Ex 70-74 to noise testing as describedabove, but use a different noise meter. The meter is a NC10 audioacoustic analyzer (Neutrik Cortex Instruments) that analyzes noise by ⅓octave frequency bands rather than full octave bands as with the CELnoise analyzer. This effectively triples the number of frequency bandsamplings. Begin testing at a frequency of 1 Hz, with a 30 secmeasurement time, fast function, equipment setting EXP EC, and minimumrange using a microphone placed 15 mm from the film rather than 17 mm asin previous testing. Summarize the test results in Table 26.

TABLE 26 Noise Level in dB(A) by Ex No. Freq (Hz) 70 71 72 73 74  6323.7 24.0 25.1 25.2 30.4  80 29.2 28.5 20.2 21.0 22.8 100 22.5 22.7 22.524.5 25.2 125 26.7 26.9 27.8 29.8 28.6 160 32.7 32.7 33.7 35.7 33.9 20039.0 38.6 38.8 41.1 36.7 250 43.0 42.0 42.7 43.8 38.2 315 45.3 43.4 45.245.2 38.6 400 46.6 46.2 45.9 45.8 40.5 500 46.3 46.2 45.8 46.0 41.2 63045.0 44.3 44.7 45.6 40.7 800 44.3 43.8 44.2 45.3 40.2 1000  44.7 4.3744.2 44.9 39.2 1250  44.9 44.1 44.1 45.9 39.2 1600  45.9 44.9 45.6 47.740.7 2000  51.7 50.4 52.1 54.1 46.1 2500  50.0 50.1 50.3 52.4 47.1 3150 43.6 45.1 45.1 45.8 42.7 4000  40.2 42.1 43.0 42.7 39.9 5000  40.2 42.143.0 43.0 36.3 6300  38.3 39.5 39.8 39.2 31.7 8000  32.9 37.4 34.7 36.830.0 10000  27.6 32.2 27.9 26.8 26.0 12500  21.9 27.3 20.8 21.2 18.216000  16.1 21.3 8.9 13.5 7.6

The data in Table 26 show that the multilayer films of Ex 70-74 havepotential utility as quiet films based upon the noise ratings thatpredominantly fall below 50 dB(A) over the frequency range shown inTable 26.

Subject the films of Ex 70-73 to barrier testing and summarize theresults in Table 27.

TABLE 27 Chemical Test* Units Ex 70 Ex 71 Ex 72 Ex 73 H₂S Permeabil-Cm³/m²- 23.6 8.8 5.9 4.9 ity day H₂S B.T. Sec 455 575 695 1010 DEDS B.T.Min 194 270 151 179 3-methyl B.T. Hrs 100 45 110 120 indole *Perm =permeability; B.T. = breakthrough time

The data in Table 27 show that the multilayer films of Ex 70-73 havebarrier properties similar to or better than the film of Comp Ex C.Films 71-74 containing the B-100 co-polyester have significantly lowerpermeability to H2S than film 70.

Determine heat seal properties as in Test 9 for Ex 72 and 73, and, forEx 70-73, modulus as in test 5 and elongation at break (Elong @ Break)and break stress in accord with test 9 (ASTM F88)in both the machinedirection (MD) and transverse direction (TD). Ex 72 has a film/film sealstrength of 22.3 N/25 mm at a sealing temperature of 182° C. and 23.6N/25 mm at 193° C. Ex 73 has a film/film seal strength of 20.9 N/25 mmat a sealing temperature of 193° C. and film/LDPE seal strengths of 9.8,16.9 and 18.7 N/25 mm at respective sealing temperatures of 138° C.,149° C. and 171° C. Summarize remaining physical property test resultsin Table 28 and provide the test data for multilayer films of Comp Ex Aand Comp Ex D, the latter two representing films currently used infabricating ostomy bags.

TABLE 28 Comp Comp Test Ex 70 Ex 71 Ex 72 Ex 73 Ex A Ex D Elong @ BreakMD(%) 328 330 293 443 450 465 Elong @ Break TD(%) 350 369 449 485 483533 Break Stress MD(MPa) 19.5 19.6 18.8 21.7 25.1 18.0 Break StressTD(MPa) 16.2 17.3 15.4 17.5 17.2 14.3 1% Secant Modulus 250 292 223 149170 120 TD(MPa) 1% Secant Modulus MD 210 285 218 148 160 120 (MPa) Sealstrength film/film n.d. n.d. 22.3 n.d. 27.7 21.3 MD(N/25 mm) n.d. = notdetermined

Table 28 shows that the films of Ex 70-72 have satisfactory filmphysical properties similar to those of Comp Ex A and D. Other filmstructures that fall within the scope of the present invention shouldprovide similar results.

Ex 75 and Comp Ex AG

Prepare a two-layer co-extruded film wherein one layer contains PET-Gand has a thickness of 12 μm and the other layer contains EVA-3 and asadditives, 0.2 wt % erucamide, 0.2 wt % stearamide and 0.1 wt % silicondioxide, all percentages based on layer weight, and having a thicknessof 38 μm.

Use a two layer film laminate similar to a commercial TDDS backing layerfilm as Comp Ex AG. The laminate has an overall thickness of 50.8 μm,including a 12 μm thick layer of a polyester such as polyethyleneterephthalate and the balance being a layer of an ethylene-vinyl acetatecopolymer.

The laminate of Comp Ex AG has a 2% modulus in both MD and TD that issignificantly higher than that of the film of Ex 75, perhaps as much asdouble that of Ex 75, if not more. At the same time, the laminate ofComp Ex AG has an Elongation at Break in both MD and TD that issubstantially lower than that of the film of Ex 75, often less thanone-half that of the Ex 75 film.

The film of Ex 75 should provide a barrier to chemicals contained in aTDDS device or patch equivalent to that of the laminate of Comp Ex AG ornearly so. At the same time, the film of Ex 75 should provide greatercomfort to one who wears the patch as a result of the lower modulus. Thelower modulus of Ex 75 also promotes improved, relative to Comp Ex 75,patch conformability to a wearer's skin. The coextruded film of Ex 75should also have a lower tendency to delaminate than the Comp Ex AGlaminate.

What is claimed is:
 1. A multilayer film structure that comprises atleast one quiet film layer having noise dampening properties, said quietlayer comprising at least one polymer resin or polymer resin compositionhaving a Tangent Delta value of at least 0.25 at a temperature withinthe range between −5° C. and 15° C. or at least 0.32 at a temperaturewithin the range of from −12° C. to −5° C., and at least one secondlayer having a storage modulus G′ equal to or greater than 2×10⁴ N/cm².2. The multilayer film of claim 1, wherein the second layer comprises apolymer selected from an amorphous thermoplastic polyester or a blend ofessentially amorphous thermoplastic polyesters, a glycol-modifiedpolyester, polyethylene terephthalate or polybutylene terephthalate,ethylene-vinyl alcohol polymers, polycarbonates, polyvinyl alcohols,styrene-acrylonitrile copolymers, acrylonitrile-butadiene-styreneterpolymers, poly(methyl methacrylate), styrene-butadiene copolymers,polyacrylonitrile, a polyamide or co-polyamide selected from PA-6,PA-6,6, PA-11, and PA-12, amorphous polyamides, MXD6 polyamide,polyvinylidene chloride, vinlylidene chloride-vinyl chloride copolymers,vinylidene chloride-methylacrylate copolymers, PHAE, polyurethanes,epoxies, PEN, syndiotactic polystyrene, and polystyrene.
 3. An articleof manufacture fabricated from the film of claim 1, the article beingselected from ostomy bags, trans-dermal delivery systems, cosmeticpatches, incontinence bags, medical collection bags or parenteralsolution bags, odorous food packaging or protective clothing.
 4. Amultilayer film structure that comprises at least one quiet film layerhaving noise dampening properties, said quiet layer comprising at leastone polymer resin or polymer resin composition selected from lowcrystallinity polypropylene, a blend of an amorphous poly (alpha-olefin)and a random propylene homopolymer or copolymer, ethylene-styreneinterpolymer or polynorbornene in an amount of 25 weight percent or moreand having a Tangent Delta value of at least 0.25 at a temperaturewithin the range between −5° C. and 15° C. or at least 0.32 at atemperature within the range of from −12° C. to −5° C., and at least onesecond layer having a storage modulus G′ equal to or greater than 2×10⁴N/cm².
 5. The multilayer film of claim 4 wherein the amount is 30 weightpercent or more.
 6. The multilayer film of claim 4, wherein the secondlayer comprises a polymer selected from an amorphous thermoplasticpolyester or a blend of essentially amorphous thermoplastic polyesters,a glycol-modified polyester, polyethylene terephthalate or polybutyleneterephthalate, ethylene-vinyl alcohol polymers, polycarbonates,polyvinyl alcohols, styrene-acrylonitrile copolymers,acrylonitrile-butadiene-styrene terpolymers, poly(methyl methacrylate),styrene-butadiene copolymers, polyacrylonitrile, a polyamide orco-polyamide selected from PA-6, PA-6,6, PA-11, and PA-12, amorphouspolyamides, MXD6 polyamide, polyvinylidene chloride, vinlylidenechloride-vinyl chloride copolymers, vinylidene chloride-methylacrylatecopolymers, PHAE, polyurethanes, epoxies, PEN, syndiotactic polystyrene,and polystyrene.
 7. An article of manufacture fabricated from the filmof claim 4, the article being selected from ostomy bags, trans-dermaldelivery systems, cosmetic patches, incontinence bags, medicalcollection bags or parenteral solution bags, odorous food packaging orprotective clothing.